We synthesized NixFey@Pdz/C core–shell nanoparticles with different compositions to investigate their activity for glycerol oxidation. EDS and ICP analyses revealed divergences between the nominal and experimental compositions of the catalysts, indicating that the synthesis route was a little inefficient for depositing Ni-Fe. However, the addition of Ni-Fe to Pd increased its activity in glycerol oxidation. The Ni1.5Fe13.5@Pd85/C catalyst presents superior electrocatalytic performance, with a specific activity 1.28 times greater than that of Pd/C. In situ FTIR spectroscopy data revealed favorable formate and CO2 production on NiFe@Pd/C catalysts. Our research highlights the synergistic effect of composition and core–shell morphology on catalytic activity.