The new design is generally based on the improvement of existing commercial photoinitiators as well as the introduction of new building blocks aimed at improving the properties of polymerized materials. A photoinitiator named 1,4-bis(4-bromophenyl)-2,5-bis(4-(trifluoromethyl)phenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (PyBF) with a symmetric trifluoromethyl (-CF3) end groups was synthesized through a one-step aldehyde–ketone condensation reaction. The -CF3 groups are introduced on the 2,5-position phenyl rings of the pyrrolo[3,2-b]pyrrole core, and PyBF shows visible light photoinitiation ability that matching with light-emitting diode (LED) of 405 nm. Both acrylate prepolymer and monomer have been applied to our photopolymerization formulas using PyBF as one-component photoinitiator. The thermal stability of PyBF is compared with commercial photointiator (diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, TPO) with a comparable thermal decomposition temperature (Td) temperature above 300 oC. The SEM results show that the cured materials of PyBF/TPO/PEGDA mixture using PyBF/TPO as two-component photoinitiator system have smooth surface, instead of PyBF/PEGDA and TPO/PEGDA systems. Therefore, both the potential pyrrole-based one- and two-component photoinitiator for rational design is worth expected for visible light photopolymerization.