New photoinitiator systems of dimethylphenacylsulfonium butyltnphenylborate (DMPSB) as a donor-acceptor initiator and styryl dyes have been investigated for free radical polymerization of an acrylate with visible lasers (488, 514 and 647 nm). DMPSB was able to be sensitized by many styryl dyes. When polymerized with pentaerythrithol triacrylate, the sensitivity value of the photosensitive layer containing DMPSB was higher than that of an tetrabutylammonium butyltnphenylborate (TBAB) as an electron donating initiator or a dimethylphenacylsulfonium tetrafiuoroborate (DMPS) as an electron accepting initiator. The sensitivity values of the photosensitive layer containing the photoinitiator systems had a close relation to the free energy changes between the excited singlet styryl dyes and DMPSB.