The gas diffusion layer (GDL) of polymer electrolyte membrane fuel cells plays a key role in controlling moisture in these cells. When the GDL is exposed to a cold environment, the water droplets or water nets in the GDL freeze. This work observed the supercooling and freezing behaviors of water droplets under low temperature. A GDL made of carbon fiber was coated with a waterproof material with 0%, 40%, and 60% PTFE (polytetrafluoroethylene) contents. The cooling process was investigated according to temperature, and the water droplets on the GDL were supercooled and frozen. Delay in the supercooling release was correlated with the size of water droplets on the GDL and the coating rate of the layer. Moreover, the supercooling degree of the droplets decreased as the number of freeze-thaw cycles in the GDL increased.