The fabrication of highly active and stable Pt-based catalysts is an essential factor for the large-scale development of direct methanol fuel cells (DMFC), which is currently hampered by inefficient metal utilization, vulnerability to the CO poisoning effect, and relatively sluggish reaction kinetics. Herein, porous graphene with morphology-controlled TiO₂ supported Pt nanoparticles (UV-Pt@TiO₂/graphene) as efficient catalysts for the methanol oxidation reaction (MOR) are investigated via an in situ UV-photo-assisted reduction strategy. It is found the TiO₂ nanorods (TONR) with the optimal (001) and (110) facets effectively strengthen the Pt trapping ability, enhance the adsorption of methanol molecules and weaken CO intermediate poisoning compared to TiO₂ nanocrystals (TONC). Importantly, both in acid and alkaline electrolytes, the UV-Pt@TONR/GN catalysts exhibit superior catalytic activity (1945.63 mA mg_Pt⁻¹/3165 mA mg_Pt⁻¹) and long term durability for the MOR, outperforming most reported electrocatalysts. The outstanding catalytic properties are intrinsically attributed to well-hierarchical structure and strong metal–support interactions, which facilitate the tuning of surface properties and electronic structures, promote charge transfer, and synergistically boost methanol electrooxidation. This work indicates the importance of catalyst morphology/facet tuning for catalytic performance enhancement and provides a feasible idea for DMFC catalyst design and construction.