Abstract Preparing biobased heat-resistant vinyl polymers remains as a big challenge. We successfully used trans -anethole (ANE), a typical natural and sustainable vinyl compound with abundant sources yet scarcely taken for preparing polymers, for preparing polymer microspheres through copolymerizing it with N -phenylmaleimide ( N -PMI). The copolymer microspheres were efficiently obtained with high yield (>87%), clean surface, good spherical morphology, and narrow size distribution (CV = 6.22%) by free radical precipitation polymerization. The content of ANE units in the copolymer was found to be approximately 50 mol%. Growth of the microspheres was investigated in detail. Glass transition temperature (Tg) and decomposition temperature of the present copolymers were up to respectively 170 and 380 °C, which cannot be achieved in normal polymeric microspheres. The present biobased microspheres are expected to find practical applications as novel thermal stable polymer materials and heat-resistant additives.