Abstract Novel glycerol crosslinked poly(methyl methacrylate)(PMMA) was synthesized in one step in the presence of cocktail of chemical initiator and the biocatalyst Novozym 435 under mild reaction conditions. The objective of the study was to investigate the feasibility of glycerol to crosslink PMMA by biocatalytic route and to explore glycerol crosslinked PMMA as controlled release vehicle Effect of reaction time, temperature, glycerol to methylmethacrylate ratio, and methacrylate to toluene ratio was studied. Glycerol crosslinked PMMA swelled 289(±9)% in acetone and collapsed when immersed in water and in hexane. Swelling and shrinking of glycerol crosslinked PMMA was reversible in nature. Nanoparticles of glycerol crosslinked poly(methyl methacrylate) were synthesized by nanoprecipitation technique. The particles were spherical and of nanosize. The nanoparticles were used for the encapsulation and release of mosquito repellent N,N-diethyl-m-toluamide. Nanoparticles could encapsulate 8.5mg of repellant in 4h. The repellant got released from the nanoparticles at a controlled rate for a prolonged time interval. Release was more pronounced in deionized water and pH 7 buffer than in acetone. Addition of 1% NaCl further improved the release profile. 80% of encapsulated repellant was released from the nanoparticles in pH 7 buffer with 1% NaCl.