There's actually not much information about whether Tito Vilanova was a smoker or not. Although he died of throat cancer, which is often linked to smoking or chewing tobacco.
I don't know if this is an indication or clue that Vilanova was a smoker, but before Tito Vilanova's death, Barcelona launched an app that helped supporters quit smoking.
It was part of the club's anti-smoking initiative, and you do have to wonder how much of Barca's involvement in the health campaign had to do with Vilanova's medical condition, and the possibility he was a smoker.
It would make sense that he would have wanted to use his position in Barca and on the international stage to raise awareness for a cause that has affeceted him personally.
Have a look at the video of Barcelona's anti-smoking campaign: