NiO/Ni multilayers were deposited alternately by reactive magnetron sputtering and conventional magnetron sputtering. Phase structure, microstructure and photoelectric properties in different annealing environments were studied. XRD and TEM results indicate that NiO and Ni layers appear alternately in as-grown multilayers. Only NiO(111) preferred orientation is found in the films after atmosphere annealing, but multilayer structure still exist in the films after vacuum annealing, whose crystallization increases obviously. Both the as-grown and vacuum annealed films show a low visible light transmittance and a resistivity as low as 10-5 Ω·cm, while the films annealed in the air exhibit a high resistivity as well as a low transmittance of 49.3%.