After oxidation of zirconium and its alloys, a metal/semi-conductor contact structure will be formed, and the photo-electrochemical method could be used to investigate the property of the structure. The applications of photo-electrochemical methods in the research of the properties of oxides formed on zirconium and its alloy surfaces were summarized, the possibility of use of photo-induced cathodic protection was discussed, and the new application of photo-electrochemical methods in the research of in-pile performance and property modification of zirconium and its alloys was put forward in the present paper.