The effects of aging temperature on the corrosion behavior of 316 L stainless steel in a simulated cathodic environment of a proton exchange membrane fuel cell (PEMFC) were investigated by potentiodynamic polarization curves, electrochemical impedance spectroscopy (EIS), double-loop electrochemical potential response (DL-EPR). The results show that the corrosion resistance of 316 L is significantly degraded after aging at 750–900 °C for 1 h in the simulated cathodic environment of PEMFC. A strong sensitivity to intergranular corrosion takes place after aging at 850 °C, and chromium rich M23C6 carbides precipitate on grain boundaries. The precipitation of M23C6 leads to discontinuity of the passivation film near the grain boundaries, resulting in Cr-depleted zones at the grain boundaries, increasing intergranular corrosion, and decreasing corrosion resistance. When the aging temperature exceeds 950 °C, grain boundary precipitation of M23C6 does not occur and the corrosion resistance is improved. At an aging temperature of 1050 °C, a dense Cr2O3 film is formed on the surface of the alloy during the polarization test, giving it the best corrosion resistance in the simulated cathodic environment of PEMFC.