We report on a successful room-temperature polymerization of 2-(hydroxyethyl)methacrylate (HEMA) under high pressure. The polymerization is observed in a limited range of pressures 0.1 to 1.6 GPa without the use of any initiator. When the compressed sample is irradiated at 488 or 355 nm by a laser, the polymerization reaction rate is increased by a factor of 10 or 30, respectively. Moreover, the shift of the laser wavelength to the UV improves the polymerization yield of the recovered sample to 84%. The catalysis of the polymerization process by light results from a one-photon-assisted electron transfer to p* antibonding states of the monomer molecule. The observed polymerization is irreversible and almost complete, which makes this synthesis process suitable for applications.