The 60-year-old beat comic Ronnie Corbett to second place followed by actor Bill Nighy, while US President Barack Obama grabbed the fourth spot.
The Prince of Wales was hailed for his sense of style depicted from his double breasted suits, by Saville Row tailors Gieves and Hawkes, to his accessories such as a pocket handkerchief, silk tie and John Lobb shoes.
"He is perfectly turned out in a double-breasted suit," News.com.au quoted the magazine judges as saying.
"Admirably, the Prince keeps his wardrobe in appropriate style: we''re told he has a room laid out like a tailor''s shop," the judges added.
The British heir to the throne also left behind tennis ace Roger Federer, actor Adrien Brody and Kuwaiti royal Sheikh Majed al-Sabah to grab the honour.
Esquire editor Jeremy Langmead said: "It''s the men who dress like grown-ups who really caught the judge''s eyes this year; as well as those who have developed their own distinctive style and stuck with it.
"I love the fact that we have such a diverse list: from artists to royals, to one of the Two Ronnies."