We present here a facile strategy for synthesis of CoPt nanoparticles supported on poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS) functionalized multi-walled carbon nanotubes (MWCNTs). The as-prepared CoPt-PEDOT:PSS/MWCNT catalyst was characterized with UV–vis spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray diffraction and X-ray photoelectron. The well-supported and low-Pt-content nanostructure catalyst exhibits superior catalytic activity for the NaBH4 hydrolysis reaction with a 47.3kJmol−1 of activation energy. The maximum hydrogen generation rate is 6900mLmin−1g−1 at 298K.