Lester is handed the pitching duties after a successful performance in the win over the Los Angeles Dodgers
Lester, 32, is handed the pitching duties after a successful performance in the National League Championship Series win over the Los Angeles Dodgers, where he was named joint Most Valuable Player.
The veteran left-hander is unbeaten in three previous World Series starts which included two wins in 2013 for the Boston Red Sox against the St. Louis Cardinals.
Lester successfully stymied the Dodgers offense in two Cubs victories in the NLCS, restricting them to just two runs over 13 innings in Games 1 and 5.
Cleveland have named right-hander Corey Kluber to start in Tuesday's opener.
"This is why they signed me, this is why they wanted me to come here, to win a World Series," Lester said after the Cubs sealed a 4-2 series defeat of the Dodgers at Wrigley Field on Saturday.
"This is why I wanted to come here. I wanted to win a World Series for this city, for this organization, for this ownership and front office.
"It's awesome to be a part of this organization and be where we're at right now."
The Cubs are bidding to end the longest title drought of any team in American sports history, having not won the World Series since 1908.
The perennial punchlines of Chicago sport had not even reached the best-of-seven World Series championship matchup since 1945.
Tuesday's opener in Cleveland gets under way at 8:00 pm (0000 GMT).