Proton exchange membrane fuel cells (PEMFCs) provide an appealing sustainable energy system, with the solid-electrolyte membrane playing a crucial role in its overall performance. Currently, sulfonated poly(1,4-phenylene ether-ether sulfone) (SPEES), an aromatic hydrocarbon polymer, has garnered considerable attention as an alternative to Nafion polymers. However, the long-term durability and stability of SPEES present a significant challenge. In this context, we introduce a potential solution in the form of an additive, specifically a core–shell-based amine-functionalized iron titanate (A–Fe2TiO5), which holds promise for improving the lifetime, proton conductivity, and power density of SPEES in PEMFCs. The modified SPEES/A–Fe2TiO5 composite membranes exhibited notable characteristics, including high water uptake, enhanced thermomechanical stability, and oxidative stability. Notably, the SPEES membrane loaded with 1.2 wt% of A–Fe2TiO5 demonstrates a maximum proton conductivity of 155 mS cm−1, a twofold increase compared to the SPEES membrane, at 80 °C under 100% relative humidity (RH). Furthermore, the 1.2 wt% of A–Fe2TiO5/SPEES composite membranes exhibited a maximum power density of 397.37 mW cm−2 and a current density of 1148 mA cm−2 at 60 °C under 100% RH, with an open-circuit voltage decay of 0.05 mV/h during 103 h of continuous operation. This study offers significant insights into the development and understanding of innovative SPEES nanocomposite membranes for PEMFC applications.