In this study, a sulfonated poly(ether sulfone) having cardo-type fluorenyl groups (FL-SPES) was investigated as a cathodic binder to improve fuel cell performance via increased the oxygen diffusion in the cathode. The maximum power density achieved by using the membrane electrode assembly (MEA) prepared with FL-SPES with a low ion exchange capacity (IEC) of 1.31 meq g–1 was 520 mW cm–2, which is more than twice as high as that of BP-SPES (210 mW cm–2) having typical biphenyl groups with a similar IEC. At high IEC of 1.55 meq g–1, the power density obtained by using BP-SPES was improved to 454 mW cm–2 but remained lower than that of FL-SPES. In addition, although the IEC, swelling degree, and specific resistance were similar to each other, the gas permeability of FL-SPES was improved by approximately three times compared to that of BP-SPES. The steric structure of cardo-type FL-SPES increased the free volume between the polymer backbones, leading to an increase in gas transfer. Consequently, oxygen diffusion was promoted at the cathode, resulting in improved fuel cell performance.