Novel catalyst layers for proton exchange membrane fuel cells (PEMFCs) were investigated by in-situ growing of Pt nanowires (Pt-NWs) on carbon matrix. The Pt-NWs grew on the matrix along the thickness direction with a length of 10–20 nm and a diameter of 4 nm. In-situ cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and polarization experiments were employed to characterize the electrochemical performance of the Pt-NWs electrodes. The results showed that the predominantly {111}-oriented facets and oxygen access of the Pt-NWs structure contribute to the higher performance in comparison with that of the conventional catalyst layers. This work is advantageous for fuel cell catalyst layer design by allowing the controlled modification of both Pt distribution and pore size.