Direct methanol fuel cells have emerged as highly promising energy conversion devices in the past few decades. However, some challenges, such as carbon monoxide (CO) poisoning and unsatisfactory long-term stability, remain for platinum (Pt) as a methanol oxidation reaction (MOR) catalyst. This review covers recent advances in Pt alloy MOR catalysts and provides some insights. This review presents MOR catalytic mechanisms based on CO or non-CO pathways. Typical dimension-based designs of MOR catalysts, such as anisotropic nanowires, metallene, nanoframes, and corresponding rationales for performance enhancements, are introduced. More importantly, some key tuning strategies are elaborated, including intermetallic compound synthesis, interface engineering, and surface facet engineering. High-entropy alloys as an intriguing class of MOR catalysts with favorable prospects are also discussed. Finally, future directions and opportunities are outlined.

Complete ethanol oxidation reaction (EOR) in C1 pathway with 12 transferred electrons is highly desirable yet challenging in direct ethanol fuel cells. Herein, PtRh jagged nanowires synthesized via a simple wet‐chemical approach exhibit exceptional EOR mass activity of 1.63 A mgPt⁻¹ and specific activity of 4.07 mA cm⁻², 3.62‐fold and 4.28‐folds increments relative to Pt/C, respectively. High proportions of 69.33% and 73.42% of initial activity are also retained after chronoamperometric test (80 000 s) and 1500 consecutive potential cycles, respectively. More importantly, it is found that PtRh jagged nanowires possess superb anti‐CO poisoning capability. Combining X‐ray absorption spectroscopy, X‐ray photoelectron spectroscopy as well as density functional theory calculations unveil that the remarkable catalytic activity and CO tolerance stem from both the Rh‐induced electronic effect and geometric effect (manifested by shortened Pt─Pt bond length and shrinkage of lattice constants), which facilitates EOR catalysis in C1 pathway and improves reaction kinetics by reducing energy barriers of rate‐determining steps (such as *CO → *COOH). The C1 pathway efficiency of PtRh jagged nanowires is further verified by the high intensity of CO₂ relative to CH₃COOH/CH₃CHO in infrared reflection absorption spectroscopy.