Three monoamino‐substituted anthraquinone derivatives (AAQs), that is, 1‐aminoanthraquinone (AAQ), 1‐(methylamino)anthraquinone (MAAQ), and 1‐(benzamido)anthraquinone (BAAQ), incorporated with various additives [e.g., triethanolamine (TEAOH) and phenacyl bromide (PhC(═O)CH2Br)] are investigated for their roles as photoinitiating systems of free radical photopolymerization of (meth)acrylate monomers upon the exposure to UV to green LEDs. The AAQs‐based photoinitiating systems, AAQ/TEAOH/PhC(═O)CH2Br and BAAQ/TEAOH/PhC(═O)CH2Br photoinitiators exhibit the highest efficiency for the free radical photopolymerization of DPGDA under the irradiation of blue LED and UV LED, respectively, which is consistent with the extent of overlap between their absorption spectra and the emission spectra of the LEDs. AAQ/TEAOH/PhC(═O)CH2Br photoinitiator can also initiate the free radical photopolymerization of different (meth)acrylate monomers, with an efficiency dependent on the chemical structures of these monomers.