Two different kinds of electron donating amines AH-Ⅰ and AH-Ⅱin combination with electron accepting diaryliodonium salts were used as a new type of photoinitiation system for radical polymerization sensitive to visible light. The AH-Ⅰ amines, such as aliphatic and aromatic amines, can only absorb light below 300—400 nm by themselves, but readily interact with iodonium salts to form a charge transfer complex (CTC), which extends the absorption largely into the visible range. The AH-Ⅱ amines, such as N-substituted derivatives of chalcone, coumarin ketone and styryl ketone, et al have a long conjugated structure and exhibit large absorbability in the visible range. These systems are stable in the dark, but rapidly undergo electron transfer reaction upon irradiation with visible light to generate initiating radicals. Both AH-Ⅰ/DPIO and AH-Ⅱ /DPIO systems can efficiently induce photopolymerization of acrylates, acrylonitrile and styrene, etc. The photopolymerization rates and related kinetic equations for several systems were studied.