Abstract Single-atom catalysts have been widely investigated for several electrocatalytic reactions except electrochemical alcohol oxidation. Herein, we synthesize atomically dispersed platinum on ruthenium oxide (Pt 1 /RuO 2 ) using a simple impregnation-adsorption method. We find that Pt 1 /RuO 2 has good electrocatalytic activity towards methanol oxidation in an alkaline media with a mass activity that is 15.3-times higher than that of commercial Pt/C (6766 vs. 441 mA mg ‒1 Pt ). In contrast, single atom Pt on carbon black is inert. Further, the mass activity of Pt 1 /RuO 2 is superior to that of most Pt-based catalysts previously developed. Moreover, Pt 1 /RuO 2 has a high tolerance towards CO poisoning, resulting in excellent catalytic stability. Ab initio simulations and experiments reveal that the presence of Pt‒O 3f (3-fold coordinatively bonded O)‒Ru cus (coordinatively unsaturated Ru) bonds with the undercoordinated bridging O in Pt 1 /RuO 2 favors the electrochemical dehydrogenation of methanol with lower energy barriers and onset potential than those encountered for Pt‒C and Pt‒Ru.