Photopolymerization of dimethylaminoethylmethacrylate (DMAEMA) is studied in bulk and in solutions in the presence of different photoinitiators using differential photocalorimetry (DPC). The rate of DMAEMA photopolymerization is slow compared to that of alkylmethacrylates. Bimodal DPC curves of DMAEMA photopolymerization in bulk are obtained. The type I photoinitiators (IRGACURE(R) 651 and IRGACURE(R) 1700), which produce free radicals by homolytic fragmentation of photoexcited molecules, are more effective in promoting photopolymerization of DMAEMA. The type II photoinitiators (benzophenone and IRGACURE(R) 500), which initiate DMAEMA photopolymerization through an H-abstraction mechanism involving an amino group from the monomer (polymer), are less efficient and favor the formation of partly crosslinked products. The effects of the photoinitiator concentration, temperature, and solvent on the kinetic data are evaluated and discussed. A scheme of photopolymerization of DMAEMA, including the formation of intermediate DMAEMA based macromonomers, is proposed. The main point of the suggested scheme is a high chain transfer to the DMAEMA monomer.