The aim of this study is to examine and evaluate several dye/amine systems as photoinitiators for photopolymerization of 2-hydroxyethyl acrylate (HEA) monomer under visible light conditions. For this purpose, a series of dye/amine photoinitiators were formed using methylene blue (MB) or acridine orange (AO) as photosensitizers, and triethanolamine (TEOA), ethyl 4-(dimethylamino) benzoate (EDMAB), trioctylamine (TOA), and N,N-diméthylallylamine (DMAA) as co-initiators. The photopolymerization kinetic of the HEA monomer in the presence of proposed dye/amine systems was performed using Fourier-transform infrared spectroscopy (FTIR) analysis and the synergetic effect of the dye/amine photoinitiators systems on the photopolymerization efficiency was examined. Interestingly, (MB/EDMAB) system shows the better reactivity with a total conversion of HEA monomer.