The PBC based hybrid organic-inorganic films were synthesized based on tetraethylorthosilicate (TEOS), titanium isopropoxide (TIP), and poly(t-butylstyrene-b-hydrogenated isoprene-b-sulfonated styrene-b-hydrogenated isoprene-b-t-butylstyrene) or pentablock copolymer (PBC) via sol-gel chemistry. A ternary phase diagram was estibalished to understand the homogeneity of TEOS-TIP sol-gel system dependent on initial sol composition and reaction conditions leading to controllable materials. All hybrid PBC-TEOS-TIP membranes exhibited higher water uptake than unmodified PBC membranes. Proton conductivity increased 80% from 58 mS/cm for unmodified PBC film to 85 mS/cm for hybrid nanocomposite film due to the role TEOS-TIP within it. This can be attributed to the partial charge transfer from the titanate’s inorganic domains to sulfonate groups that promote acid dissociation and proton attraction. The PBC’s microphase-separated morphology changed from well-ordered lamella-like structure to a random and homogenous distribution of ionic domains with increasing TIP concentration, which was observed from AFM and SAXS results. TGA analyses revealed a decrease in degradation temperature due to titanate's catalytic character, and DMA results demonstrated reduced polymer chain mobility caused by inorganic-organic interactions. Finally, these PBC-TEOS-TIP hybrid composites were used as proton-exchange membranes (PEM) for hygroden fuel cells.