In this work, the CuWO4 film based resistive switching memory capacitors were fabricated with hydrothermal and spin-coating approaches. The device exhibits excellent photo-electron double controlled resistive switching memory characteristics with OFF/ON resistance ratio of ~103. It is believed that the interface of CuWO4 and FTO is responsible for such a switching behavior and it can be described by the Schottky-like barriers model. This study is useful for exploring the multifunctional materials and their applications in photo-electron double controlled nonvolatile memory devices.