Although this link is in Spanish, you should be able to make out fairly easily who is on Venezuela's WBC roster.
The preliminary 60-man roster has some great pitchers: Johan Santana, Carlos Zambrano, Francisco Rodriguez, Felix Hernandez, and Freddy Garcia to name a few. The catchers aren't bad with Ramon Hernandez and Victor Martinez. The outfield has Bob "El Comedulce" Abreu, Magglio Ordonez, and Miguel Cabrera.
Overall, I think Venezuela will be helped out the most by having Luis Salazar as its hitting coach.