Abstract: The Corey-Bakshi-Shibata (CBS) catalyst precursor and styrene were grafted onto the surface of poly(divinylbenzene) (PDVB) microsphere by reversible addition-fragmentation chain transfer (RAFT) precipitation polymerization. Thus hairy particle-supported CBS catalyst was obtained. The structure and morphology of functional hairy particle were characterized by nuclear magnetic resonance (1H-NMR), Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). The preparation of polymer brushes using RAFT technology can effectively control the degree of graft polymerization and avoid polymer chain agglomeration, making the hairy particle-supported CBS catalyst stably dispersed in the reaction medium. The obtained hairy particle-supported CBS catalyst was used to catalyze the asymmetric reduction of acetophenone and the catalytic activity and stereoselectivity of the catalyst were investigated. The results showed that the catalyst not only had the advantages of easy separation for heterogeneous catalysts, but also those for homogeneous catalysts with high selectivity and high conversion. In the asymmetric reduction of acetophenone, with the increase of mole fraction of catalyst precursor, the enantiomeric excess (ee) value of the product phenylethanol increased. When the molar fraction of catalyst precursor exceeded 40%, the supported catalyst had excellent catalytic effect. Moreover, after five cycles the catalytic activity did not decrease significantly, ee value of the product phenylethanol was up to 93% and the conversion of acetophenone approached 100%.