New six dicarboxylic acid dimethacrylates (DMAs) were synthesized and studied as photocurable dental monomers. The photopolymerization behavior of the monomers was investigated by FTIR spectroscopy using camphorquinone (CQ) and 2-(dimethylamino)ethyl MA (DMAEMA) as a photoinitiating system. Relatively high conversions (>55%) resulted from photopolymerization of the monomers by visible light. The volume shrinkage of the monomers during photopolymerization was significantly influenced by their molecular weight and degree of conversion. Preliminary tests of the composites formulated with a dicarboxylic acid DMA, a diluent, CQ, DMAEMA, and a glass filler were carried out including a three-point bending test and fluoride release.