Photochromic (PC) ZnO nanoparticles are synthesized for the first time by using a VHF plasma enhanced CVD apparatus. The prepared ZnO film changes from transparent to PC state under UV irradiation; on being subjected to heat treatment, it changes back to transparent state. There is a threshold temperature for attaining the PC phase. The Debye-Waller factor of Zn atoms is specifically large for the PC ZnO. The ZnO nanoparticles contain carbon as impurity. The effects of C-O bonds on the ZnO crystal structure and density of states (DOS) are simulated based on density-functional theory. The results reveal that the crystal structure is slightly distorted and a sufficient DOS for PC light absorption is formed in the band gap.