The Juventus new signing gave the Old Lady the perfect start when he put them ahead early on in the first half.
But Villarreal bounced back in the second through a Dani Parejo goal to ensure the spoils were shared at the Estadio de la Ceramica.
Samuel Chukwueze started his first Champions League game of the season and played for 90 minutes but was largely anonymous throughout the tie, while 22-year-old Vlahovic needed just one shot to open his account for in what was his ChampionsLeague debut.
Vlahovic got Juventus off to the best possible start when he gave them the lead just 32 seconds into the game after superbly controlling a long ball from Danilo before firing into the far corner.
The goal saw him beat the record set by Andreas Moller back in 1995.
Villareal recovered from the early set back to dominate the rest of the opening half of the game.
However, the Yellow Submarines only came close to an equaliser on two occasions.
First, Giovani Lo Celso rattled the Juve post with a very good attempt in the 13th minute before Super Eagles’ Chukwueze sets up Arnaut Danjuma in the 16th minute.
However, an audacious flick from the Nigerian-born Dutch international gave Wojciech Szczesny problems before the Polish goalkeeper eventually saved.
That move was Chukwueze’s most notable contribution in an otherwise quiet half as Juventus went into the break with a narrow lead.
In the second half, Villareal continued from where they stopped in the first, dominating their visitors in search of the equaliser.
The Yellow Submarines for all their dominance were made to wait until the 66th minute to be rewarded with a deserved equaliser when Etienne Capoue found Parejo with a delicious pass which the Spaniard made no mistakes to volley home with a low effort.
It was not less than the hosts deserved as they were clearly the better of the two teams in the encounter.
The rest of the match turned out to be one of few good chances as both sides held on for a draw heading into the second leg in Turin.
AON