Platinum nanoparticles (NPs) protected with octylamine (OA) as well as partially replaced by controlled ratios of alkylamine with pyrene group (PA) were successfully synthesized by a two-phase liquid reduction method of Pt(IV). The NPs without any pretreatment to remove the introduced organic-protected agents have been well-characterized and applied as supported catalysts on carbon black for oxygen reduction reaction (ORR). The modification of the Pt NP surface with OA and PA significantly improved the electrocatalytic activity such as area specific and mass specific activities, whose values increased by an increase in PA ratios. The potential cycle test demonstrates that the PA modification of Pt NPs enhances the stability of the catalyst and sustains high area and mass specific activities of ORR.