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High-quality Pt-based catalysts are highly desirable for ethanol oxidation reaction (EOR), which is of critical importance for the commercial applications of direct ethanol fuel cells (DEFCs). However, most of the Pt-based catalysts have suffered from high cost and low operation durability. Herein a two-step method has been developed to synthesize porous Pt nanoframes decorated with Bi(OH)3, which show excellent catalytic activity and operation durability in both alkaline and acidic media. For example, the nanoframes show a mass activity of 6.87 A·mgPt-1 in alkaline media, which is 13.5-fold higher than that of commercial Pt/C. More importantly, the catalyst can be reactivated simply, which shows negligible activity loss after running for 180,000 s. Further in situ attenuated total reflection-infrared (ATR-IR) absorption spectroscopy and CO-stripping experiments indicate that surface Bi(OH)3 species can greatly facilitate the formation of adsorbed OH species and subsequently remove carbonaceous poison, resulting in a significantly enhanced stability towards EOR. This work may favor the tailoring of desired electrocatalysts with high activity and durability for future commercial application of DEFCs.