Addition of a bis(trichloromethyl)‐substituted‐1,3,5‐triazine (Tz) to a dye/amine photoinitiating system leads clearly to an increased efficiency of polymerization under visible light irradiation. The polymerization rates obtained with three triazine derivatives with either phenosafranine, eosin or Rose Bengal as light absorbing species, were measured. Whatever the investigated dye/amine mixture, the addition of Tz led to a strong synergistic effect: the inhibition time decreased and the polymerization rate increased significantly when the three components were used jointly. The spectroscopic and redox properties of the Tz were measured. The system dye/amine/Tz was investigated through time‐resolved laser spectroscopy and steady state fluorescence experiments. A detailed reaction mechanism was elaborated which shows that Tz acts mainly as an inhibitor scavenger. The involved inhibitor is the reduced dye (DH∗︁) arising from the first photochemical reaction between the excited states of the dye and the amine.