Carbon-supported Pt (Pt/C) catalyst was selectively functionalized with thermally responsive poly(N-isopropylacrylamide) (PNIPAM) to improve water transport in the cathode of proton exchange membrane fuel cell (PEMFC). Amine-terminated PNIPAM selectively reacted with the functional group of -COOH on carbon surfaces of Pt/C via the amide reaction by 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) as a catalyst. Pt surfaces of Pt/C were intact throughout the carbon surface functionalization, and the carbon surface property could be thermally changed. The PNIPAM-functionalized Pt/C was well-dispersed, because of its hydrophilic surface property at room temperature during the catalyst ink preparation. In sharp contrast, when PEMFC was operated at 70 degrees C, PNIPAM-coated carbon surface of Pt/C became hydrophobic, which resulted in a decrease in water flooding in the cathode electrode. Because of the switched wetting property of the carbon surface, PEMFC with PNIPAM-functionalized Pt/C catalyst in the cathode showed high performance in the high current density region. To explain the enhanced water transport, we proposed a simple index as the ratio of systematic pressure (driving force) and retention force. The synthetic method presented here will provide a new insight into various energy device applications using organic and inorganic composite materials and functional polymers.