Thanks to being eligible through his father, the one-time St Mirren striker represented the volcanic Caribbean island of Montserrat in the inaugural qualifying match, a 5-2 defeat by Belize on June 15, 2011 that was followed by a further 3-1 defeat in the return leg a month later.
As a result of there being no facilities on Montserrat capable of hosting international fixtures, they staged the CONCACAF region fixture in front of an estimated 100 people in the Ato Boldon Stadium, named in honour of the world champion sprinter, in the Trinidadian town of Couva.
Indeed, despite the defeat, it looked, for a short time at least, as though Mendes and his team-mates might progress to the second round as a result of Belize being suspended by FIFA after their government failed to recognise the national football team and refused to provide security for the visiting side or the match officials in the return leg.
In the end, the encounter was moved to neutral territory in Honduras. Mendes would, perhaps fortunately, be unable to travel.
However, as he enjoys the coverage of the finals from the comfort of his living room, the Londoner reflects fondly on the role he played in the first of 232 qualifying matches which decided the 32-team line-up in Brazil.
"Kicking off the whole qualifying tournament was brilliant," he said. "We ran Belize close and played quite well. Jay Lee Hodgson scored both our goals, but I did get an assist.
"The squad we have now is so much better. If we were the team we are now, we would have won that qualifier comfortably. One of our eligible players, Lloyd Dyer, has just joined Watford from Leicester.
"Over the years, we've had a number of eligible players, but they kept waiting for England such as Michael Duberry, Paul Furlong and Ruel Fox. I was first called up in 2004 when I was at Huddersfield, for a Gold Cup qualifier. They don't have many games, but I think I have played about 12 times.
"I'm still connected to the FA. I am now a sports scientist and I've just completed my degree. I was doing sports science for them for their Gold Cup qualifiers. I was going to play, in fact, but I picked up an injury."
Now 37, Mendes has not hung up his boots entirely, but he is keen to focus more on becoming part of a club's backroom team following his studies. He is spending this summer helping out with a programme for out-of-contract players in East Kilbride, which is being staged by football agent Tony Ashgar's company, and hopes it will lead to some form of employment.
"I'm not playing league football any longer. I finished with Nairn County after a spell up there," said Mendes, who also played in Scotland with Dunfermline Athletic and Aye United. "If they say they need me, I'll play a few games to get myself fit. I play in the holding role for them, so I don't have to run about so much.
"I'm doing my coaching badges, but I like getting players fitter and stronger. I like the science surrounding it. I got into it because, towards the end of my career, I was getting a few injuries. If I'd had the sports science at my disposal, it wouldn't have been happening.
"I wish I'd picked up on it when I was playing, but I wasn't at a top club where they were into sports science. Ten years ago, it wasn't that prevalent.
"I'm now looking for a job at a club at a decent level. I can tap into how players feel and how they think, when things are needed, when to ease back and when to push them on.
"I went into Blackburn and Manchester City to volunteer just to get some experience in it and I'm doing a bit at St Mirren at the moment. I've been gearing towards this for the last three years."