Li-doped p-type ZnO thin films were grown by using radio frequency magnetron sputtering. In our experiment, ZnO targets were fabricated by using the Li-doped ZnO powders that had been synthesized by glycine (urea)–nitrate combustion process. The structural characteristics of ZnO thin films were examined by XRD and SEM. The results showed that ZnO films possess a good crystalline with c-axis orientation, uniform thickness and dense surface. Current–voltage properties of p-ZnO:Li/n-Si structure had been examined in an effort to delineate the carrier type behavior in ZnO semiconductor. p-ZnO:Li/n-Si heterojunctions displayed rectifying behavior. As a result I–V measurements exhibited a polarity consistent with the Li-doped ZnO being p-type.