Despite tremendous progress has been achieved in the past two decades, the lack of high-performance catalysts suitable for long-term operation remains a great challenge in realizing the commercial application of direct methanol fuel cell technology. Here, we reported a simple approach for one-pot synthesis of PtCu alloy nanoframes along with their exciting electro-catalytic performance for methanol oxidation. PtCu alloys with highly-open nanoframe structures have been achieved in presence of a structure-directing agent like polyvinyl pyrrolidone (PVP) and reducing solvent like sodium borohydride. Such PtCu alloy nanoframes show tremendous improvement in the methanol electrooxidation with a highest mass activity of 1.64 A mg(Pt)(-1) (much lower onset potential compared to Pt alone), which is believed to be much higher compared to that of the commercial Pt/C catalyst and most of the literature reports, indicating a better alloy formation and highly active sites created by highly open nanoframes structures. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.