As an alternative to the oxidative acid treatment, a noncovalent π–π interaction method is employed to deposit Pt electrocatalysts on highly hydrophobic carbon nanofibers (CNFs) for the application of polymer electrolyte membrane (PEM) fuel cells. Three different functionalization agents, namely benzyl mercaptan (BM), 1-aminopyrene (AP), and 1-pyrenecarboxylic acid (PCA), are used to functionalize CNFs and the effect of these groups on the electrochemical properties is examined. While the BM and AP act as a poison to Pt catalyst, the functionalization of CNF with PCA improves the distribution and loading of Pt as well as reducing the sintering of Pt particles. From the carbon corrosion test, unlike the oxidative acid treatment, the PCA treatment sustains the corrosion resistance of CNFs because it preserves the intrinsic properties of CNFs without damaging their surface structure. Therefore, the PCA treatment is a very effective way to prepare catalysts for PEM fuel cells and also extended to the fabrication of graphitized-carbon-supported catalysts of other precious metal for various applications.