2-(2-Methoxyethoxy) ethyl methacrylate (MEO2MA) and polyethylene glycol methyl ether methacrylate (OEGMA500) were used as monomers, the temperature-sensitive random copolymers P(MEO2MA-co-OEGMA500) were synthesized by free radical polymerization with horse radish peroxidase (HRP)/acetylacetone (ACAC)/H2O2 catalytic initiator system. The number-average molecular weight, molecular weight distribution, the structure and thermal properties of the synthesized polymers were characterized by GPC, 1HNMR, FTIR and DSC. The temperature-sensitive properties of the synthetic polymers were characterized by the determination of light transmission and particle size of polymer aqueous solution at different temperatures. Temperature-sensitive polymer with a feed molar ratio of n(MEO2MA):n(OEGMA500) of 100:0, 95:5, 93:7, 90:5, and 85:15 were synthesized. The results show that the LCST of the synthetic polymers increases from 24 ℃ to 39 ℃ and the glass-transition temperature of the synthetic polymers gradually decreases from -11.75 ℃ to -14.74 ℃ with the increase in the feed proportion of OEGMA500. The LCST decreases with increasing the concentration of polymer aqueous solution. With the increase of the temperature, the average particle size of the polymers increases and are 82.5~135.6 nm larger than that at low temperature.