The photochemical and electrochemical investigations of commercially available, safe, and cheap fluorescent brighteners, namely, triazinylstilbene (commercial name: fluorescent brightener 28) and 2,5‐bis(5‐tert‐butyl‐benzoxazol‐2‐yl)thiophene, as well as their original use as photoinitiators of polymerization upon light emitting diode (LED) irradiation are reported. Remarkably, their excellent near‐UV–visible absorption properties combined with outstanding fluorescent properties allow them to act as high‐performance photoinitiators when used in combination with diaryliodonium salt. These two‐component photoinitiating systems can be employed for free radical polymerizations of acrylate. In addition, this brightener‐initiated photopolymerization is able to overcome oxygen inhibition even upon irradiation with low LED light intensity. The underlying photochemical mechanisms are investigated by electron‐spin resonance‐spin trapping, fluorescence, cyclic voltammetry, and steady‐state photolysis techniques.
