Ionic liquids (ILs) modified solid catalysts are considered to be an effective method for constructing efficient electrocatalytic interface. In order to investigate the cationic impacts of ILs on Pt surface towards the oxygen reduction reaction (ORR) performance, herein we selected and synthesized [NTf2]- based two hydrophobic protonic ILs ([EIM][NTf2], [BIM][NTf2]) and two hydrophobic non-protonic ILs ([EMIM][NTf2], [BMIM][NTf2]), and the synthesized ILs were used to modify the commercial Pt/C catalyst surface. Among the imidazolium-based hydrophobic ILs used in this study, the ORR activities of the protonic ILs modified catalysts were all higher than those of the non-protonic ILs modified catalysts, with the catalyst modified by 1-butylimidazolium bis(trifluoromethanesulfonyl)imide ([BIM][NTf2]@Pt/C) having the highest activity. The ORR half-wave potential in the acidic half-cell is as high as 0.913 V (vs. RHE), increasing the mass activity to 1.73 times than that of commercial Pt/C and the specific activity to 3 times than that of commercial Pt/C, while reaching a half-wave potential drop of only 12 mV after 5000 cycles, the performance is still higher than that of commercial Pt/C. Further material characterization and electrochemical tests were performed on the catalysts showed that the enhanced electrocatalytic activity of [BIM][NTf2]@Pt/C was attributed to the increased number of active sites on the Pt surface from the ILs modification, which enhanced plasmon and mass transfer on the Pt surface, and effective inhibition of Pt nanoparticle solubilization, thus enhancing the ORR activity and stability. This study deepens the understanding of the synergistic electrocatalytic mechanism at the ILs@Pt interface and provides a theoretical basis for the design of next-generation high-efficiency fuel cell catalysts.