Benzaldehyde / Cp2TiCl2 / nano-zinc system could catalyze radical polymerization of styrene. The polystyrene with a contolled/living character was obtained. In benzaldehyde / Cp2TiCl2 / nano-zinc system, in order to dicuss how every factor would affect the radical polymerization of styrene, the equivalent of Cp2TiCl2, nano-zinc, and benzaldehyde was changed. The condition of 0.5 / 4 / 8 / 100 revealed a living radical polymerization, the polystyrene polymer chain was growth with conversion linearly and agree to the theoretical molecular weight, the polystyrene had low polydispersities index (PDI). The polystyrene-b-polycaprolactone was synthesized by ring opening polymerization of ε-caprolacotone from polystyrene. Because benzaldeyde could inititate radical polymerization and ring opening polymerization, the idea was futher utilized in the synthesis of PSt-b-PCL in one-pot reaction. In one-pot reaction, 0.5 / 4 / 4 / 300 / 60 was better condition compared with other ratios. In order to get polystyrene-b-polycaprolactone which had narrow dispersities, utilizing strategy of chain extension of polystyrene at different temperature from polycaprolactone. Chain extension of polystyrene at 90° C from polycaprolactone was better results compared with 75° C and 110° C.