The 29-year-old passed an extensive medical after a knee problem saw him fail an initial examination and threatened to scupper the move.
"My goal here is to play in the Champions League," Naldo, who played consistently in the competition during his seven-year spell with Werder, told the club's website. "I had a great time in Bremen but I want to get back to the Champions League. Wolfsburg's for me and I am very happy to be here."
Naldo, who was out for 16 months after suffering a knee injury two years ago, insisted he never doubted he would be able to prove his fitness.
"I was positive. My knee felt good and I know my own body," added Naldo, who had a light training session with his team-mates on Thursday.
The Wolves finished eighth in the Bundesliga last season, 16 points behind the top four, and coach Felix Magath claimed the new acquisition would boost his squad.
He said: "I am very happy that we have been able to sign such an exceptionally good central defender. His statistics are very impressive.
"He hasn't just proven himself to be a very strong defender, he can also prove a threat to the opposition's defence. Those are qualities we haven't had in the team in the past and I am quite sure that at Wolfsburg we can make big steps forward together with Naldo."