The potential of onion‐like carbon (OLC) as an efficient alternative carbon support for palladium‐decorated manganese dioxide (Pd‐MnO2) catalyst for the electro‐oxidation of glycerol in alkaline medium is reported. Pd‐MnO2/OLC and Pd‐MnO2/C (where C denotes activated carbon or Vulcan carbon XC‐72) catalysts and their corresponding reference monometallic catalysts (Pd/OLC and Pd/C) are synthesized by a microwave‐assisted solvothermal procedure. Electrochemical measurements clearly prove that OLC, contrary to the state‐of‐the‐art Vulcan carbon XC‐72, is able to promote the electrocatalytic performance of Pd and Pd‐MnO2 towards the oxidation of glycerol in alkaline medium (in terms of decreased onset potential, large current density, and fast electron transport). Incredibly, the current density of the OLC‐based system is more than 150 % greater than their corresponding activated carbon‐based counterparts. These highly insightful results of Pd‐based catalyst are correlated with the synergistic effects of the ternary nanohybrid materials promoted by the unique intrinsic physico‐chemical properties of OLC.