A facile and fast synthesis of poly(2-hydroxyethyl methacrylate) (PHEMA)/silica hybrid was achieved using in situ polymerization method under microwave irradiation, in which the polymerization of 2-hydroxyethyl methacrylate (HEMA) was carried out together with the sol-gel reaction of methyltrimethoxysilane (MeTMOS). The preparation rate of the hybrid under microwave irradiation was accelerated rapidly relative to that under conventional heating due to the activation of hydroxyl groups of HEMA and silanol groups of alkoxysilanes by microwave irradiation. When acetic acid was used as a catalyst for the sol-gel reaction of MeTMOS, the transparency of the hybrid was improved. The transparency, homogeneity, and formability of the hybrid prepared under microwave irradiation were better than those prepared under conventional heating. In addition, it was found that the degree of polymerization of HEMA under microwave irradiation is higher than that under conventional heating by using FT-IR spectroscopy due to the activation of the polymerization of HEMA. Thermal properties of the hybrids prepared under microwave irradiation were almost identical to those under conventional heating.