Porous carbon fibers play a pivotal role in electrochemistry due to their unique structural and textural properties, offering a promising avenue for diverse applications ranging from energy storage to electrocatalysis. In this study, we investigate the intricate relationship between the electrochemical responses of porous carbon fibers synthesized using the Design of Experiments protocol and their textural properties, aiming to elucidate key insights for material design and optimization. Through comprehensive correlation analyses, we uncover notable associations between oxygen reduction reaction mass activities and capacitances measured at different polarization rates, highlighting the significance of pore accessibility in dictating electrochemical performance. While direct correlations with specific surface area and total pore volume for mass activities were not observed, our findings reveal significant trends regarding capacitance retention. Specifically, materials with an elevated specific surface area and total pore volume demonstrate enhanced capacitance retention, particularly under varying charging and discharging rates. These results underscore the importance of optimizing specific surface area and pore volume to maximize capacitive performance across diverse operating conditions. Our study provides valuable guidance for developing porous carbon fibers tailored for superior electrochemical performance in various applications.