The research of active and stable electrocatalysts toward liquid fuel oxidation reaction is of great significance for the large-scale commercialization of fuel cells. Although explosive efforts have been devoted to pursuing high-performance nanocatalysts for fuel cells, both the high cost and sluggish reaction kinetics have been two major drawbacks limited its commercial development. In this regard, we demonstrated a facile solvothermal method for the syntheses of an advanced class of PtCu nanocatalysts with unique pentangle-like. By combining the merits of high surface active area, as well as the synergistic and electronic effects, the as-prepared pentangle-like Pt3Cu nanocatalysts showed superior electrocatalytic activity towards ethylene glycol oxidation with the mass and specific activities of 5162.6 mA mg-1 and 9.7 mA cm-2, that ∼ 5.0 and ∼ 5.1 times higher than the commercial Pt/C, respectively. More significantly, the Pt3Cu pentangle also exhibited excellent long-term stability with less activity decay and negligible change in structure after 500 cycles, showing a novel class of anode catalysts for fuel cells and beyond.