The catalyst intrinsic area-specific activity for the oxygen reduction reaction (ORR) was constrained by the scaling relations governing the adsorption of reaction intermediates. In this study, we strategically modified the electronic band structures of Pt(CuNi)x alloy nanoparticles by varying their composition, resulting in a specific activity trend resembling a volcano shape. The introduction of MoOy shattered the existing scaling relations, leading to a significant enhancement in ORR activity of Pt alloys, surpassing the activity of Pt(CuNi)x catalysts. These findings proved the effectiveness of MoOy deposition on Pt(CuNi)x in disrupting the scaling relations, ultimately improving ORR activity. Display omitted •MoOy-Pt(CuNi)x heterojunction structured nanoparticles were synthesized.•All samples showed significant improvement in oxygen reduction reaction activity.•MoOy-Pt(CuNi)0.66 showed exceptional 5.0 mA/cm−2Pt ORR activity at 0.9 V vs. RHE.•The creation of dual active sites significantly promoted ORR kinetics.