Schottky diodes based on ZnO nanorods, undoped and co-doped with different concentrations (0.0, 0.2, 0.4, 0.6 and 0.8 at.%) of Ce and Sm, were fabricated on glass and on n-Si (111) substrates using chemical bath deposition assisted with the sol-gel spin coating. The ZnO maintained its hexagonal shape up to higher levels of doping (0.8 at.%) with the growth rate being suppressed by Ce and Sm co-doping. The as-synthesized nanorods were found to be highly crystalline and no impurities or peaks related to Ce and Sm or their oxides were observed. Room temperature Raman spectroscopy revealed that the prominent E2 high peak shifted towards a lower wave number and the intensity decreased upon doping. X-ray photoelectron spectroscopy studies at room temperature showed that the presence of Zn and O in all samples with small amounts of Ce and Sm being detected at doping levels of 0.8 at.%. Photoluminescence studies at room temperature revealed a weak ultraviolet emission and a strong deep level (visible) emission. Deconvolution of the visible emission spectra showed that more than one defect contributed to the visible emission. The I–V characteristics of the fabricated Schottky diode devices measured at room temperature showed that the Ce and Sm co-doping increased the generation-recombination process in the fabricated Schottky diodes. Furthermore, the current transport mechanism in the fabricated Schottky devices at a lower voltage (0.0– 0.6 V) was dominated by ohmic conduction mechanism, while at voltages greater than 0.6 V, the space charge limited current and the trap filled limit voltage mechanism dominated.