In the present study, crosslinked poly(vinyl alcohol) (PVA) membranes were prepared at different temperatures using poly(styrene sulfonic acid-co-maleic acid) (PSSA_MA) (PVA:PSSA_MA = 1:9). The hybrid mem-branes were prepared by varying the TEOS content between 5 and 30 wt%. The PSSA_MA was used both as a crosslinking agent and the hydrophilic group donor ($-SO_3H$ and/or-COOH). The proton conductivity increased with up to 20 wt% TEOS, but decreased above this level, although the water content decreased with increasing TEOS content. This result suggests that the silica doped into the membrane improved the formation of proton-conduction pathways due to the absorption of molecular water. The PVA/PSSA_MA/Silica containing TEOS 20% showed both high proton conductivity (0.026 S/cm at $90^{circ}C$) and low methanol permeability ($5.55{ imes}10^{-7}cm^2/s$).