ZnO/Graphene nano-films were directly prepared on Cu substrate via a low pressure chemical vapor deposition (LPCVD) and sol-gel method. The effects of the annealing temperature on the structural, morphology, the chemical state and component, and optical property of these ZnO/Graphene nano-films were investigated. The XRD patterns demonstrate that the ZnO/Graphene nanostructures exhibit the hexagonal wurtzite structure and the crystalline quality increases with increasing the annealing temperatures from 500 to 700 ℃. When the annealing temperature reaches at 700 ℃, SEM analysis shows that sample ?lm exhibits dense and uniform grains and smooth surface and the average grain size of film deposited 3 layers is about 35.7 nm. The PL measurement confirms that ZnO/Graphene nano-film deposited 3 layers at the annealing temperatures of 700℃ has an better optical performance, which due to the higher crystalline quality and lower defect concentration.