This study investigates the phenomenon of water freezing below the freezing point in polymer electrolyte fuel cells (PEFCs). To perform in-situ observation of the fuel cell, a system capable of simultaneously observing inside the fuel cell with visible and infrared images was developed. Liquid water transportation was confirmed at -10ºC when remaining water was purged enough inside the fuel cell before cold starting. The water generated on the gas diffusion layer expanded inside the gas flow channel with the water temperature at approximately -10ºC. Upon freezing, the water temperature rose significantly. This result indicates that the water is in a super-cooled state. Based on these results, it is confirmed that it is possible to generate a fuel cell maintaining water in a super-cooled state and that fuel cell performance is dramatically improved by keeping the water in such a state.