To investigate the degradation mechanism of the as-prepared Pd/C catalyst, in situ and ex situ accelerated stress tests were carried out via potential cycling. Durability tests of the single cells with Pd/C catalysts were performed through an interval constant current density mode. Electrochemical impedance spectroscopy (EIS) was applied to measure the impedance of the single cell during degradation tests. Results indicate that the degradation of Pd/C catalyst may be attributed to the phase transition of absorbed α-phase PdH to β-phase PdH, the dissolution of Pd metal, and the size increase of Pd nanoparticles. Moreover, the degradation of single cell may be predominantly ascribed to the degradation of catalyst, the deterioration of contact between electronic/ionic conductors, as well as the flooding of gas diffusion channels.