Sulfonated poly(phthalazinone ether sulfone ketone) (SPPESK) membranes and sol-gel derived SPPESK/silica hybrid membranes have been investigated as potential polymer electrolyte membranes for direct methanol fuel cell (DMFC) applications. In comparison with the SPPESK membrane, the SPPESK/silica membranes exhibited higher water content, improved proton conductivity, and lower methanol permeability. Notably, the silica embedded in the membrane acted as a material for reducing the fraction of free water and as a barrier for methanol transport through the membrane. From the results of proton conductivity and methanol permeability studies, we suggest that the fractions of bound and free water should be optimized to obtain desirable proton conductivities and methanol permeabilities. The highly sulfonated PPESK hybrid membrane (HSP-Si) displayed higher proton conductivity (3.42 ${ imes}$ 10$^2$ S/cm) and lower methanol permeability (4.15 ${ imes}$ 10$^$7/ $ extrm{cm}^2$/s) than those of Nafion 117 (2.54 ${ imes}$ 10$^2$ S/cm; 2.36 ${ imes}$ 10$^$6/ $ extrm{cm}^2$/s, respectively) at 30$^{circ}C$. This characteristic of the SPPESK/silica membranes is desirable for future applications related to DMFCs.