According to the gelatification of sodium hydroxide ethanol solution, the chitosan (CS)/polyvinylpyrrolidone (PVP) composite hydrogel microspheres have been prepared in this paper. Meanwhile, the influence of PVP content and PH on the swelling property and the adsorption Cr(Ⅵ) effect of CS/PVP hydrogel microspheres has been also discussed. The results have shown that the introduction of PVP has significantly improved the swelling property of CS. When the CS content is 2.5% and the PVP content is 5%, the swelling rate of microspheres will be the maximum. The swelling property and the adsorption property of microspheres have shown certain pH sensitivity. And the SEM has also indicated that the inside of CS/ PVP composite hydrogel microspheres is the loose network structure, which is conducive to the swelling and the adsorption.