A novel Pt@ZnO nanorod/carbon fiber (NR/CF) with hierarchical structure was prepared by atomic layer deposition combined with hydrothermal synthesis and magnetron sputtering (MS). The morphology of Pt changes from nanoparticle to nanorod bundle with controlled thickness of Pt between 10 and 50 nm. Significantly, with the increase of voltage from 0 to 0.6 V (vs. standard calomel electrode), the prompt photocurrent generated on ZnO NR/CF increases from 0.235 to 0.725 mA. Besides, the Pt@ZnO NR/CF exhibited higher electrochemical active surface area (ECSA) value, better methanol oxidation ability and CO tolerance than Pt@CF, which demonstrated the importance of the multifunctional ZnO support. As the thickness of Pt increasing from 10 to 50 nm, the ECSA values were improved proportionally, leading to the improvement of methanol oxidation ability. More importantly, UV radiation increased the density of peak current of Pt@ZnO NR/CF towards methanol oxidation by additional 42.4%, which may be due to the synergy catalysis of UV light and electricity. (c) 2017 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.