The widespread deployment of microbial fuel cells (MFCs) is limited by high fabrication costs and low power output. This investigation focuses on overcoming these drawbacks by employing clayware-based proton exchange membranes modified with sulfonated-titanium nanotubes (s-TNTs). Specifically, membranes with varying compositions of s-TNT (5–10%) and montmorillonite (0–20%) were fabricated and their properties were rigorously evaluated. Results showed that MFCs with s-TNT membranes significantly outperformed pristine clayware membranes, with a high ion transport number of 0.85 and minimal oxygen diffusion. In particular, the T10 membrane supported the highest chemical oxygen demand removal efficiency of 83.67 ± 0.66%, coulombic efficiency (26.71 ± 0.66%), power density (152.10 ± 1.2 mW/m2), and lowest internal resistance of 88.75 ± 1.6 Ω. These findings highlight the potential of s-TNT-enhanced clayware membranes to deliver superior performance for both wastewater treatment and energy recovery, making them a suitable option for large-scale MFC applications. [Display omitted] • Fabrication of sulfonated titanium nanotubes (s-TNT) modified clayware membrane. • Membrane incorporated with s-TNT achieved ion transport number of 0.85 • Clayware membrane with 10% (w/w) s-TNT (T10) achieved 26.71% coulombic efficiency. • The T10 membrane delivered 152.10 mW/m2 power density, 2.62-times of pure clayware. • s-TNT-modified membrane are suitable for large-scale microbial fuel cell applications. [ABSTRACT FROM AUTHOR]