The Hilton-owned chain claims the Millionaire game is the first by a UK bookmaker to offer a prize this big.
Customers in Ladbrokes' 1875 shops can bet £2 to predict the scores of 20 Premier League or Football League matches, with a range of cash prizes available.
The game will be promoted extensively in the outlets and window displays, using the strapline 'Play it, win it, live it'. Created by Geoff Howe Marketing Communications, the campaign will develop over the 10 months of the season. The first poster depicts an ecstatic winner resigning by phone from a tropical location.
Ladbrokes marketing manager David McMorrow said the brief was to grab maximum attention in the shortest time. A large proportion of high-street gambling is spontaneous betting, making the stores' window displays crucial.
According to Ladbrokes, football betting is the fastest-growing sector for bookmakers. The chain set up a fantasy football website during Euro 2004, and as a result holds details of more than 200,000 potential football punters.