We report on a one-step hydrothermal approach to synthesize Sulfonated Silica-Ceramic Carbon Electrode (HT-SS-CCE), a Nafion-free catalyst layer (CL) structure for proton exchange membrane fuel cells (PEMFC). This new approach to HT-SS-CCE synthesis gave rise to a more uniform distribution of the silicate within the CL and stabilizing the Pt nanoparticles (NPs) which further enhanced the activity and durability of electrode. In the initial assessment of the catalyst under three electrode cell experiments, the HT-SS-CCE showed enhanced activity towards the oxygen reduction reaction (ORR) compared with Nafion-based Pt/C. Furthermore, the HT-SS-CCE preserved a greater portion of its initial performance after the accelerated stress testing (AST) compared with Nafion-based Pt/C. This translated into higher performance and durability for HT-SS-CCE in fuel cell testing.