Li-doped, p-type ZnO thin films have been realized via dc reactive magnetron sputtering. An optimized result with a resistivity of 16.4Ωcm, Hall mobility of 2.65cm2∕Vs, and hole concentration of 1.44×1017cm−3 was achieved, and electrically stable over a month. Hall-effect measurements supported by secondary ion mass spectroscopy indicated that the substrate temperature played a key role in optimizing the p-type conduction of Li-doped ZnO thin films. Furthermore, ZnO-based p-n homojunction was fabricated by deposition of a Li-doped p-type ZnO layer on an Al-doped n-type ZnO layer.