In restorative dentistry, acrylamide monomers bearing phosphonic acid moieties have proved to be useful species for the formulation of dental self-etch adhesives since they provide enhanced adhesion to hydroxyapatite and are not subject to hydrolysis, thus potentially improving their adhesive durability. Previous studies have demonstrated that phosphonic acid acrylamides increase the rate of photopolymerization of diacrylamide monomers. To understand whether this rate acceleration is specific to the acrylamide function of the monomer, or due to the phosphonic acid group per se, or is applicable only with a crosslinking reaction, we have synthesized several acrylamide and methacrylate monomers bearing phosphonic acid or phosphonate moieties and studied their photopolymerization kinetics. The acrylamide phosphonic acid was found to accelerate the polymerization rate but similar monomers bearing a phosphonate ester group had a much smaller effect. A similar accelerating effect was observed when the phosphonic acid-based monomers were copolymerized with a monofunctional acrylamide monomer, excluding the possibility that the rate acceleration might be related to the crosslinking process. This rate effect is also observed when a nonpolymerizable organic phosphonic acid is present in the polymerizing medium. We suggest that the increase of the medium polarity is responsible for this rate enhancement effect. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013