The development of high-performance catalytic nanomaterials is important to implement sustainable and electrochemical energy devices of alkaline fuel cells, metal–air batteries, and electrolyzers in the envisaged energy-transition scenarios. Synthesizing effective nanocatalysts as both anode materials for oxidation of glycerol (byproduct of the biodiesel industry) and cathode materials for the oxygen reduction reaction (ORR) is still a bottleneck. Herein, we report palladium-based nanomaterials whose physicochemical and electrochemical properties are tuned by the judicious choice of the support (rGO, Vulcan XC72R), the addition of a coelement (Fe), and the structure (alloy/core–shell). The bimetallic-based electrode shows a drastically enhanced electrocatalytic performance with a beneficial shifting of the onset potential, production of high currents, and good durability for both the ORR (kinetic current density jk = 2 mA cmPd–2 or 1 A mgPd–1) and glycerol oxidation (jp = 2.3 mA cmPd–2 or 1.11 A mgPd–1 at the peak), higher than those of commercial catalysts and existing literature values. The present results also provide new fundamental insights about the accurate measurement of the kinetic metrics of the ORR by employing a rotating-disk (-ring) electrode setup in alkaline electrolytes with metallic catalysts. Indeed, the anodic scanning of the electrode from a low potential to a higher one results in an ultrafast electrochemical kinetics with a positive shift of the half-wave potential of ΔE1/2,anodic/cathodic = 60 mV from the cathodic direction to the anodic one. The kinetic current density dramatically increases, jk,anodic = 19.0×, 6.9×, 3.4×, and 2.4× jk,cathodic at 950, 900, 870, and 850 mVRHE, respectively. The advantage of the synthesis methodology relies on the nonuse of organic molecules as capping agents and surfactants in order to produce bare (ligand-free) bimetallic PdFe electrocatalysts with a clean catalytic surface in a facile and straightforward way.