The ruthenium-based electrocatalysts supported on carbon black were prepared by the decarbonylation of the transition metal carbonyl with the 1,6-hexanediol as the solvent. The catalysts were characterized via X-ray diffraction (XRD), transmission electron microscopy (TEM) and high resolution TEM (HRTEM). The electrochemical behaviours of the catalysts were investigated by cyclic voltammetry (CV) and rotating disk electrode (RDE) measurements in 0.5 M H2SO4 solution. The catalysts demonstrate attractive catalytic activity towards the ORR. The catalyst is expected to be promising alternative non-Pt electrocatalysts for PEMFC.