High performance nanomaterial catalysts have attracted great attention on the application for the direct alcohol fuel cell. To improve the catalytic behavior, it is a challenge to modulate the surface structure and morphology of catalysts. We integrated properties of advanced networks nanostructure and core@shell structure to form a series of PdAg@Pd worm-like networks catalysts. Importantly, the composition-optimized Pd76Ag24 WNWs exhibited excellent catalytic performance towards ethanol oxidation reaction compared to that of commercial Pd/C catalysts in alkaline media. The mass activity of Pd76Ag24 WNWs is 3.55 times higher than that of commercial Pd/C catalysts for EOR. Moreover, the Pd76Ag24 WNWs also showed superior stability after 250 successive cycles and kept far higher residual activities than that of the other catalysts. The synthesis of PdAg@Pd worm-like networks catalysts provides a reference to well combine the advantages of core@shell and networks structure to form high performance catalysts application for DEFC. (C) 2020 Elsevier Inc. All rights reserved.