Pt-based nanomaterials are proven as one of the most efficient catalysts for direct alcohol fuel cells. However, it is a challenge to construct Pt-based catalysts with high catalytic activity and less Pt. In this work, we develop a new strategy to prepare threedimensional (3D) nanonetwork structures (NNWs) like hollow Pt(Au)Cu (3D h-Pt(Au)Cu NNWs). 3D Cu nanonetworks (3D Cu NNWs) were firstly synthesized as template, and then by replacing Cu with Pt precursors or Pt and Au precursors, 3D h-Pt42Cu58 NNWs and 3D h-Pt38Au17Cu45 NNWs were obtained. Among the NNWs and commercial Pt/C, the 3D h-Pt38Au17Cu45 NNWs owned the best catalytic activity for methanol, ethanol and ethylene glycol oxidation reaction with the mass activity of 6.12 A mgPt −1, 8.53 A mgPt −1 and 12 A mgPt −1, which are 3.84-fold, 7.35-fold and 4.23-fold higher than that of commercial Pt/C. The study provides a simple strategy for preparing novel 3D hollow Pt-based polymetallic nanostructures, showing great potential in synthesizing and designing high-efficiency Pt-based electrocatalysts.