The crystalline properties and complexing ability of the amphiphilic star-shaped poly-styrene(S)-polyoxyethykne(E) block Copolymers were studied. The results show that crystal-linity increases with increase of E content or molecular weight of the copolymers. The sphe-rulites observed by quenching their melt at 20℃ or casting from CHCl3 solution appear more regular than quenching their melt at 0℃ or casting from ethylbenzene solution. These new copolymers show some mesomorphic phenomeni in toluene solution. UV spectra indicate that they can complex with picrate of alkali metals and enhance the solubility of the salt in CHCl3 or toluene.