Exploring cost-effective electrocatalysts for the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) have been a goal in the sustainable hydrogen-based society. Although abundant of alternative materials have been developed, Pt/C remains the most efficient electrocatalyst for the ORR and HER. Nevertheless, improving the stability and reducing Pt loading for Pt-based electrocatalysts are still big challenges. Herein, semiconductor crystals Na4Ge9O20 with richer topology structure was chosen as electro- catalyst support, subsequently, the conductive polymer polyaniline (PANI) was decorated on semiconductor Na4Ge9O20, low-content Pt nanoparticles (Pt NPs) with the size of 1-3 nm were then uniformly anchored on the surface of Na4Ge9O20-PANI to obtain the efficient bifunctional electrocatalyst for ORR and HER in the acidic solution. More importantly, the stability and mass activity of the obtained electrocatalyst 5 wt% Pt/Na4Ge9O20-PNAI are significantly higher than that of commercial 20 wt% Pt/C for ORR and HER. It was proposed that the PANI could not only promote the electron transfer from Na4Ge9O20 to Pt, but also stabilize the Pt NPs, thus, improving the electrocatalytic activity and stability of 5 wt% Pt/Na4Ge9O20-PNAI. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.