The ionomer content in the catalyst layer is a crucial design factor that affects the performance of polymer electrolyte membrane fuel cells (PEMFCs). However, the optimal ionomer content can vary based on the surrounding humidity levels. This study systematically evaluated the influence of the ionomer-to-carbon (I/C) ratio (0.00, 0.55, and 0.91) on PEMFC performance under fully humidified (RH 100%) and low-humidity (RH 25%) conditions. Membrane-electrode assemblies (MEAs) were fabricated using a spray coating technique, and their electrochemical properties were analyzed through polarization curves and electrochemical impedance spectroscopy (EIS). Under RH 100%, the MEA with an I/C ratio of 0.55 achieved the highest peak power density of 519.8 mW/cm², indicating a successful balance between proton conductivity and gas transport. Conversely, under RH 25%, the best performance of 203.9 mW/cm² was observed at an I/C ratio of 0.91. This shift is attributed to improved water retention at higher ionomer content, which reduced membrane dehydration and lowered both ohmic and Faradaic resistances. These findings highlight the dual role of the ionomer in facilitating proton transport and managing water balance, emphasizing the necessity of optimizing the I/C ratio according to operating conditions for stable and high-performing PEMFC operation.