Gas diffusion layer(GDL) in PEMFC performs the discharge of water vapor smoothly. When GDL is revealed to cold environment, the freezing of the water droplet or water net in GDL occurs. The purpose of this work is to observe the cooling and freezing behavior of the water droplet which meets to the microporous surface and air under the various low temperature conditions. GDL was coated with waterproof material, which has three types of coating rate, 0, 40 and 60%. Water droplets in series of sizes on GDL were supercooled, frozen and crystalized orderly by circulating low temperature brine. The process of cooling was investigated with the temperature and the snapshot of the water droplet.