The Portuguese manager, fired by the Blues in March, believes the tie would be "magnificent", while Emmanuel Adebayor was full of praise for strike partner Jermain Defoe
The Blues, who beat Tottenham 4-2 earlier this year, were knocked out of the group stages of the Champions League, and Villas-Boas does not believe their failure should be rewarded.
"When I was in Europa League with Porto, people asked me [this] a lot," the Portuguese told reporters.
"I think it's extremely unfair because the clubs that should come down are the clubs that qualify for the last 16 and then are knocked out in the last 16. That's much fairer.
"You can't give a bonus to teams who have failed, and in the situation as it stands, teams fail in the Champions League and are promoted to the Europa League which is a massive bonus."
Tottenham and Chelsea cannot meet in the last 32, but could been drawn together in the latter stages of the tournament, a prospect Villas-Boas would relish.
He continued: "Sometimes it's destiny. Hopefully if we go through we can meet each other, they have a team that can win the trophy, they will be in the late stages.
"If we cross it will be two magnificent games for sure."
Spurs qualified for the knock-out rounds by beating Panathinaikos 3-1 at White Hart Lane, and Emmanuel Adebayor was effusive in his praise of strike partner Jermain Defoe after the game.
"I think Jermain is a good player, a great striker," the Togo international told ITV Sport.
"For me, playing alongside him, I'm just learning every day and [we're] trying to know each other better and that's what we're doing.
"Today we had a chance to play together and we have done the job, everyone is happy, and now we look forward."