Insufficient activity and instability (poisoning) of Pt-based electrocatalysts for methanol oxidation and oxygen reduction reactions (MOR/ORR) impede the development of direct methanol fuel cells. Here, CoWO₄ nanoparticles-loaded WO₃ microrods coated by a thin carbon-layer are used as Pt-supports/co-catalysts for MOR/ORR. WO₃ grows along the (110) crystal plane to form microrod (diameter of ~0.6 um), which is coated by a carbon-layer (~5 nm). Pt-CoWO₄/WO₃@NCL-mr (850 ℃) shows a higher mass activity (2208 mA mg^-1_pt) than the commercial Pt/C (659.4 mA mg^-1_pt). CoWO₄/WO₃ heterojunction on the microrod surface with abundant oxygen vacancies allows the generation of surface-adsorbed hydroxyl to facilitate CO elimination and regeneration of the occupied Pt active-sites (promising stability). Pt-CoWO₄/WO₃@NCL-mr (850 ℃) has higher half-wave (0.46 V) and onset (0.54 V) potentials than Pt/C (0.41 and 0.50 V) for ORR. The microrod structure of CoWO₄/WO₃@NCL facilitates the dispersibility of Pt NPs to increase the utilization of Pt active sites and relieve the self-aggregation of Pt to obtain a promising synergy between Pt and CoWO₄ (Co²⁺) for ORR in acid media. This study provides insights not only into the synthesis of acid-resistant WO₃@NCL microrod as active Pt co-catalyst, but also into the effective utilization of surface oxygen vacancies and Co²⁺ for MOR/ORR.