Abstract Platinum nanoparticles (Pt NPs) were decorated on vanadium pentoxide nanowires (V 2 O 5 NWs) to form the core-shelled vanadium-platinum nanowires (Pt@V 2 O 5 NWs) and their electrochemical activities for methanol oxidation were investigated. The synthetic procedure involved the synthesis of abundant vanadium pentoxide nanowires (V 2 O 5 NWs) by a direct vapor-solid growth process (VS method), followed by atomic layer depositions (ALD) of platinum nanoparticles (Pt NPs) onto the V 2 O 5 NWs. After the physical examinations, three designed deposition parameters (50, 100 and 150 cycles) of Pt NPs onto the V 2 O 5 NWs by ALD process were successful. From the measurements of current-voltage (I–V) and cyclic voltammetry (CV) curves respectively, both the conductivity and the ratio of the forward anodic peak current (I F ) to the reverse anodic peak current (I R ) are enhancing proportionately to the deposition cycles of ALD process, which denotes that coating Pt atomic layers onto V 2 O 5 nanowires indeed improves the catalytic performances than that of pure V 2 O 5 nanowires.