The duo left the training ground together and were heading back to Milan from Appiano Gentile, when their vehicle was in collision with another car.
The female driver of the other vehicle is in hospital, but the two players escaped with little more than bruising.
The incident appeared to have left its mark on the duo, with coach Hector Cuper saying: "They are both safe, but shaken up and truly scared."
Goalkeeper Toldo, who signed from Fiorentina in the summer, has a minor head injury while defender Materazzi suffered a blow to his leg, but both are expected to face Parma on Sunday.
