The former Real Madrid boss left the Santiago Bernabeu at the end of last term, and has since joined returned to Stamford Bridge for a second spell at the club.
Having been under his guidance during his first tenure with the Blues, Villas-Boas is certain that the spotlight will be firmly on Mourinho.
"It won't be possible to take your eyes away from Mourinho," said Villas-Boas.
"One of his characteristics - and I don't say it in a negative way - is to deviate attentions, positive and negative, in such a way that the team is only worried about winning."
During his first stint at Chelsea, Mourinho enjoyed two Premier League title successes and five major trophy triumphs.