After a first-round bye, the draw pits Vezzali against either Japan's Shiho Nishioka or Hong Kong's Lin Po Heung.
But it would not be until the final that she would have to face either team-mate Elisa Di Francisca, who beat her at last year's European Championships, or Korean Nam Hyun-hee, whom she beat 6-5 for gold at the Beijing 2008 Games.
Even though she is world number one, Vezzali is seeded second to Nam.
And the Italian's Games will actually start early, having been chosen to carry her country's flag at the Opening Ceremony.
'It is very hard to describe what I felt when I knew I was going to be the flag-bearer,' Vezzali said.
'I feel very responsible for this role as I'm representing Italy, but I also know that as soon as the ceremony is over I will return to the athletes' village and focus on the event.
'I just hope I will not stumble.'
Mariel Zagunis, who became USA's first Fencing gold medallist for 100 years in Athens eight years ago and then retained her women's Individual Sabre title in 2008, does not start her campaign until 1 August. Her first fight is against Indonesia's Diah Permatasari.
Richard Kruse, Great Britain's standout hope for a first Olympic Fencing medal since 1964, will begin his bid in the men's Individual Foil on Tuesday against Russian Artur Akhmatkhuzin, ranked six places below him at 21st, in the last 32.