We investigated the effect of the substrate temperature on the electrical and the optical properties of ZnO/4H-SiC structures. The n-type ZnO layer was grown on p-type 4H-SiC substrate by pulsed laser deposition to form p-n hetero-junction diode structure. The n-type ZnO thin films were deposited by pulsed laser deposition at different temperatures of 200, 400, and 600 °C, respectively. It was shown from transmission line method (TLM) and auger electron spectroscopy (AES) data that the sheet resistance of ZnO on SiC was increases from ~760 Ω/square to ~4000 Ω/square as the deposition temperature increases and the oxygen outdiffusion decreases. The I-V characteristics with and without illumination has also been studied.