In this study, an electrochemical model was incorporated into a two-phase model using OpenFOAM® (London, United Kingdom) to analyze the two-phase flow and electrochemical behaviors in a polymer electrolyte membrane water electrolyzer. The performances of serpentine and parallel designs are compared. The current density and overpotential distribution are analyzed, and the volume fractions of oxygen and hydrogen velocity are studied to verify their influence on the current density. The current density decreases sharply when oxygen accumulates in the porous transport layer. Therefore, the current density increased sharply by 3000 A/m2 at an operating current density of 10,000 A/m2. Maldistribution of the overpotential is also observed. Second, we analyze the behaviors according to the current density. At a low current density, most of the oxygen flows out of the electrolyzer. Therefore, the decrease in performance is low. However, the current density is maldistributed when it is high, which results in decreased performance. The current density increases abruptly by 12,000 A/m2. Finally, the performances of the parallel and serpentine channels are analyzed. At a high current density, the performance of the serpentine channel is higher than that of the parallel channel by 0.016 V.