We studied on the synthesis of chloromethylated polystyrene as a precursor of optically active polymers for direct resolution of optical isomers. Changing the degree of crosslinking and the kind of crosslinking agents, several polystyrene resin matrices were synthesized. The matrices were chloromethylated with methylal and chlorosulfonic acid as chloromethylating agents. The effects of solvents of various dielectric constants on the chloromethylation were quantitavely examined. We also synthesized chloromethylated polystyrene of macroreticular type that retained large surface area and good physical stability. The differences between the macroreticular type and macroporous type were investigated.