Directly monitoring the oxygen reduction reaction (ORR) process in situ is very important to deeply understand the reaction mechanism and is a critical guideline for the design of high-efficiency catalysts, but there is still lack of definite in situ evidence to clarify the effect between adsorbed intermediates and the strain/electronic effect for enhanced ORR performance. Herein, in situ surface-enhanced Raman spectroscopy (SERS) was employed to detect the intermediates during the ORR process on the Au@Pd@Pt core/shell heterogeneous nanoparticles (NPs). Direct spectroscopic evidence of the *OOH intermediate was obtained, and an obvious red shift of the *OOH frequency was identified with the controllable shell thickness of Pd. Detailed experimental characterizations and density functional theory (DFT) calculations demonstrated that such improved ORR activity after inducing Pd into Au@Pt NPs can be attributed to the optimized adsorbate-substrate interaction due to the strain and electronic effect, leading to a higher Pt-O binding energy and a lower O-O binding energy, which was conducive to O-O dissociation and promoted the subsequent reaction. Notably, this work illustrates a relationship between the performance and strain/electronic effect via the intermediate detected by SERS and paves the way for the construction of ORR electrocatalysts with high performance.