Connery, who recently turned 78, is pictured sitting on a rough wooden landing stage on a beach near his home in the Bahamas with a waterproof version of Louis Vuitton's Keepall travel bag next to him.
The strapline for the ad, created by Ogilvy & Mather, reads: "There are journeys that turn into legends. Bahamas islands, 10:07".
It is the sixth in a series of portraits shot by Annie Leibovitz for Louis Vuitton's Core Values campaign, on the theme of travel as a personal journey.
Louis Vuitton is making a donation to the Climate Change Project, spearheaded by Nobel Peace Prize winner Al Gore, on behalf of Connery.
Other celebrities to have been photographed by Leibovitz in the campaign include: Andre Agassi and his wife Steffi Graf; Catherine Deneuve; Keith Richards; Sofia Coppola and her father Francis Ford Coppola; and Mikhail Gorbachev, last head of state of the USSR who contributed to the end of the Cold War with perestroika and glasnost.
Antoine Arnault, head of communications at Louis Vuitton, said: "We are extremely proud that an actor of such immense stature should have agreed to participate in Louis Vuitton's Core Values campaign."
Pietro Beccari, senior vice president of communication and marketing at Louis Vuitton, said: "Our aim was to broaden the idea of travel beyond its geographical dimension and the campaign has achieved this in a truly remarkable way.
"We are particularly proud of the acclaim it has received from within the advertising industry, witnessed by numerous awards."
The ad will appear in major international titles from October 30.
