Here, the ultrafine Pt/Pd bimetallic nanoparticles (Pt/Pd NPs) were synthesized and decorated on the multi-walled carbon nanotubes (MWCNTs) modified glassy carbon electrode (GCE) for hydrogen evolution. Pt/Pd NPs were synthesized through the reduction of their metal salt mixture with ten-butylamine as reductant and polyvinylpyrrolidone as protectant. Under the observation of transmission electron microscopy (TEM), the well dispersed Pt/Pd NPs exhibit the ultrafine size of about 13 nm diameter with the good crystallinity corresponding to the (1 1 1) planes of face-centered cubic (fcc) Pt and the (200) planes of fcc Pd. The scanning electron microscopy (SEM) also shows the dispersion and anchor of Pt/Pd NPs in the matrix of MWCNTs. Electrochemical study confirms the good electrocatalytic hydrogen evolution of Pt/Pd-MWCNT in 0.5 M H2SO4, exhibiting a potential application in the future for hydrogen based energy transformation and storage. (C) 2015 The Electrochemical Society. All rights reserved.