The door to the old house in rural Perthshire that belongs to John Wills and Pinkie Maclure has a brass knocker shaped like a smiling sun.

The welcome from its residents is equally warm.

Pumajaw, alias vocalist Maclure and electronic instrumentalist Wills, usher me into their home and out of the rain, offering hair-dryers, blankets and cups of tea before we’ve so much as exchanged introductions. We spend the afternoon by an open fire in a house that is also a recording studio for their genre-bending avant-pop, and a workshop for their stained-glass “day job”. It’s a building for which they left London, then Anstruther – and an idyllic retreat that keeps them, only just, from leaving us for Paris. “It’s great, we can do everything here,” smiles Londoner Wills. “We couldn’t really ask for more.”

You wonder if the neighbours know about them in the local shop. About Maclure’s late-80s tenure as a contemporary of Bjork and PJ Harvey; about her fleeing Banff for France on the back of a teenage Jacques Brel fascination (she is still drawn to Paris); about her extraordinary voice – parts Juliette Greco, Lydia Lunch and Ella Fitzgerald – a voice that would, in a better world, deliver the greatest Bond theme ever.

You wonder if they realise that Wills – once of psychedelic drone-rockers Loop – is possessed of an uncanny knack for bewitching atmospheres and ritualistic beats. Or that the duo’s alliance has won them fans from Radio 3 to Marie Claire (who decreed Pumajaw “disarmingly beautiful”).

They’re set to release their new album, Demon Meow Meow, in November.

It’s their third studio LP as Pumajaw, (an embellished acronym of the duo’s initials), although they’ve also recorded as Pinkie Maclure, Pinkie Maclure and John Wills, Hello and Lumen. Previous Pumajaw albums have, to quote Maclure, “been lumbered with the folk tag” – and it bears noting that they’ve collaborated with Alasdair Roberts and James Yorkston, and released music on King Creosote’s Fence Records.

But there’s no mistaking the electricity at the heart of Demon Meow Meow. It harnesses industrial electro, embraces cutting-edge technology and heralds a dramatic, revitalised lease of life.

“We spent three years writing this album,” Wills recalls. He swapped acoustic strings for an electric guitar (“a Dylan moment; a Judas moment,” laughs Maclure), and she now filters her signature concertina via effects pedals. “We went down a lot of cul-de-sacs, threw away tons of stuff – it was a big transition period,” says Wills, “but it’s getting quite a bit of radio play, and it feels like people like this better than anything else we’ve done.”

“I was a bit bored with where I was on the album before this,” admits Maclure. “The thing that originally made me start singing was pretty wild singers – jazz singers and blues singers and Bulgarian singers and experimental singers and all these kinds of incredible singers with these incredible voices. And I sort of found with the folkier thing that it was getting narrower, and the dynamics were getting flatter, and I just thought, I need to go back and think about this. We both did, didn’t we?” Wills nods in agreement. “It was like, hang on a minute – we’ve kind of lost our identity.”

It’s tempting to align the duo’s early progression from machine noise to pastoral forms with their relocation from London to the Scottish sticks 10 years ago. But both Wills and Maclure suggest their move into (and now away from) acoustic music was largely down to circumstance and technology, rather than landscape.

“When we got to Scotland, people were just kind of picking up guitars and playing songs and we thought, ‘Oh that’s really quite nice that you can just do that, let’s try that,’” remembers Maclure. “We hadn’t been able to do that before, doing electronic stuff. But now, as technology’s progressed, it’s made a massive difference.”

“Yeah, we can do everything really,” elaborates Wills. “We can go back to what we were doing years ago – we can perform virtually anything we’ve recorded – whereas before, the electronic stuff live was more like karaoke,” he shudders.

Demon Meow Meow reasserts their standing as genre-defying conductors of electro, chanson, avant-jazz, art-rock, raw blues and psychedelic pop.

They proclaim to be “stubborn as hell”, but their art is not fashioned at the expense of melody, accessibility, or songs. “I never really like things when they sound normal – no, not normal – ordinary,” Wills attests. “But I do like the idea that a song is a song; that it could just be played on the back of a table. So I think the essence of us is the same. It’s just all the noises that go round us that change.”

“The change in musical direction was also a response to the financial crisis and political climate and some of the lyrics are about that,” adds Maclure. “It seemed time to make a bit of a noise about things.”

Maclure’s stark lyrics and outstanding larynx certainly command attention. Has she received much vocal training? “Not really,” she shrugs. “I did go for some lessons with this amazing woman called Linda Hirst,” she says of the classical vocalist who also sang with Ivor Cutler. “This was in the late-80s when I was being really experimental.” (Maclure’s screaming 1980s treatise, Blue Chevrolet, is worth hunting down).

“Linda did really way-out stuff, and I went to see her because I wanted to free myself up a bit, and get away from style boundaries.”

Maclure continues. “It was fantastic – you find you can do all of these things with your voice – but I got bored after a while. I just thought, ‘I want to sing songs!’” She parodies a stroppy teenager. “Songs, please!” she deadpans. Wills chuckles along.

Much is made of the artistic chemistry – alchemy, even – between Wills and Maclure, and it’s equally striking to meet them in person. They harmonise in conversation; start and finish each other’s sentences; help each other find their points. Yet they never butt in; don’t talk over each other. It’s a pleasure to hear them share their tales of how a Juliette Greco show blew their minds (“she was awesome, so inspiring – even better than Patti Smith”); or how they forged a side-line in stained-glass to give them a “day job” that would fund their music.

“We practised stained-glass in a squatted school in Tottenham when we lived there,” explains Wills. “And then we moved to this derelict workshop in a dodgy old building in Cellardyke,” adds Maclure. “We specialise in dilapidated buildings,” they laugh. That and making music that is anything but ordinary.

Pumajaw play tonight at Stereo, Glasgow, and on November 5 at Voodoo Rooms, Edinburgh; Demon Meow Meow is out on November 7, visit www.pumajaw.co.uk