Country-rock (wing-mirror) is to be sold at Sotherby's in London on June 30 and is expected to go for in the region of £9million.
Doig, who was born in Edinburgh but grew up in Canada and lives in New York and Trinidad, had a major and acclaimed exhibition at the National Galleries of Scotland last year.
More than 20 of his paintings have sold for more than £1.5m but to date his two most expensive paintings at auction have been Road House, sold in New York in May this year for £7.04m and The Architect's Home in the Ravine, sold in London in 2013 for £7.7m.
The painting features a tunnel painted with a rainbow, a feature on the Don Valley Parkway in Toronto.
Cheyenne Westphal, head of contemporary art at Sotheby's, said: "The rainbow tunnel is one of the most prominent and resonant motifs in Doig's oeuvre.
"For lovers of Doig, it has a supreme status - akin only perhaps to that of the canoe - and of all the works in which the motif appears, the Country-Rock series is the apogee.
"Doig is a giant in the current market, and this particular work is fabled.
"Its appearance at auction represents an all-time first - and hugely exciting - opportunity for collectors."
Painted in London, the picture shows the decoration on the tunnel, which mysteriously first appeared above an underpass alongside the city's Don Valley Parkway in 1972 when Doig was growing up in Canada.
In this painting, the tunnel is seen from the passenger seat of a car, and the title is the soundtrack to the journey.
Meanwhile experts have discovered a previously unknown painting by French artist Paul Gauguin.
Bonhams said that no trace of Bouquet De Roses existed before it was contacted by the anonymous seller of the oil on canvas.
The still life is expected to fetch up to £1.2m when it goes on sale later this month.