Ru-based electrocatalysts were synthesized by the simple one-step solvothermal synthesis method. Catalytic process of oxygen-related species on the surface of the catalysts was investigated by cyclic voltammetry. The oxygen reduction reaction (ORR) activity of Ru-Se/C catalyst, obtained by rotating disk electrode (RDE) technique in O-2-saturated 0.1 M HClO4 solution, was considerably higher than that of Ru-S/C and Ru/C. Moreover, Ru-Se/C exhibited the outstanding methanol-resistant performance in mixed electrolyte of HClO4 and MeOH. The electrochemical result of Ru-Se/C obtained by RDE technique showed the ORR took place by a four-electronic charge transfer process (n = 4e).