Pb/Ni multilayer coatings, with either Pb or Ni as the top layer, were brush plated on ANSI 304 stainless steel to improve its performance as bipolar plates in polymer electrolyte membrane fuel cells (PEMFC). Surface morphology and cross-sectional microstructure of the coatings were characterized with scanning electron microscope (SEM) and optical microscope, respectively. The corrosion resistance of brush plated coatings in a simulated PEMFC environment was investigated using both three-electrode method and immersion of 300 h. Coating surfaces after the immersion were characterized with energy dispersive X-ray spectrometer (EDS). The results show that the multilayer coatings were smooth, dense, and small in grain size with clear layered structure. In the simulated PEMFC environment, the corrosion of multilayer coatings was mainly uniform corrosion. Coatings with different top layers exhibit different corrosion behaviors. Ni layer was corroded preferentially as the anode while the Pb layer was protected.