We have designed and synthesized a polyaniline (PANI)-decorated Pt/C@PANI core-shell catalyst that shows enhanced catalyst activity and durability compared with nondecorated Pt/C. The experimental results demonstrate that the activity for the oxygen reduction reaction strongly depends on the thickness of the PANI shell and that the greatest enhancement in catalytic properties occurs at a thickness of 5 nm, followed by 2.5, 0, and 14 nm. Pt/C@PANI also demonstrates significantly improved stability compared with that of the unmodified Pt/C catalyst. The high activity and stability of the Pt/C@PANI catalyst is ascribed to its novel PANI-decorated core shell structure, which induces both electron delocalization between the Pt d orbitals and the PANI pi-conjugated ligand and electron transfer from Pt to PANI. The stable PANT shell also protects the carbon support from direct exposure to the corrosive environment.