Yes, of course PSV has great motivation when they were able to beat Liverpool and with that they also have the ambition to continue racing in the Champions League. Juventus must certainly be aware of PSV's collective style of play because if they are careless, they will party again. Motta's presence at Juventus did not have a significant impact so it is difficult to guarantee that they will be able to talk a lot in the elite European competition. But the draw that brought these two teams together is of course very balanced.
When it comes to European competition, there's doubting the fact that Juventus have a better record against Dutch club PSV and when it comes to the quality of players in the two teams at the moment, Juventus is visibly ahead of PSV however, the performance of the Italian club this season isn't convincing enough for anyone to think that they're favorites to win the play-off tie against PSV.
Thiago Motta has already shown that he's got a great tactical strength to succeed at Juventus but I think he really needs to do better before he can achieve his dreams.