<p>Glycerol electrooxidation uses active and long-lasting anodes to combine the production of sustainable electricity with the value-adding of a bioderived feedstock. We report Pd–Co nanoparticles made by straightforward chemical reduction on graphitic carbon nitride (Pd_xCo_y/g-C₃N₄) with adjustable Pd/Co ratios. The g-C₃N₄ exhibits well-dispersed domains, according to structural and surface analyses. Performance in alkaline glycerol is controlled by composition: an intermediate Pd/Co ratio (Pd₅₀Co₅₀) exhibits the lowest charge-transfer resistance and stable chronoamperometric currents over ~ 10³ s, increases activity (mass activity of 4.13&#xa0;mA mg⁻¹_Pd and current density of 0.285&#xa0;mA cm^− 2 in CV at 50 mV s^− 1; 0.051&#xa0;mA cm^− 2 in LSV at 5 mV s^− 1), and decreases onset potential (-0.12&#xa0;V). Compared with other Pd_xCo_y/g-C₃N₄ catalysts investigated, Pd₅₀Co₅₀/g-C₃N₄ delivers superior activity and durability, highlighting the critical role of Pd/Co ratio optimization. This enhanced performance arises from the optimal Pd-Co alloying effect, which induces favorable electronic modulation of Pd active sites and improves the adsorption–desorption balance of glycerol oxidation intermediates. These findings demonstrate that Pd/Co ratio engineering on g-C₃N₄ offers a scalable path to economical, effective anodes for the electrooxidation of glycerol.</p> Graphical Abstract <p></p>