Polymer electrolyte membrane fuel cells were analyzed to investigate changes in the structure of the flow field and operating conditions. The cell performance, which was controlled by adjusting the width of the cathodic channel, improved as the backpressure increases. With the anodic and cathodic flow channels mismatched, the maximum power densities at 3.0 bar for a narrow cathodic channel were 1115 and 1024 mW/cm2, and those for a wide cathodic channel were 959 and 868 mW/cm2, respectively. The diffusion characteristics were investigated using the non-dimensional numbers Re (Reynolds), Sc (Schmidt), and Sh (Sherwood) to confirm the improvement of mass transport. The narrower the channel or the higher the operating pressure, the larger Re was and the smaller Sc and Sh became. In particular, the wider the anodic channel, the larger the value of Sh.