The development of potential and novel proton exchange membrane (PEMs) is imperative for further commercialization of Direct Methanol Fuel Cell (DMFC). In this study, flat sheet hybrid membrane as an alternative PEM made up of polyvinyl alcohol (PVA) and mesoporous phosphotungstic acid-Silica (mPTA-Si) at various loadings of 0.5, 1.0, 1.5 and 2.0 wt% was prepared to examine the desirable properties for DMFC application. The characteristic test such as water uptake and proton conductivity were conducted. As the mPTA-Si loading increases, the proton conductivity of PVA/mPTA-Si membrane increased up to 1.81 x 10-3 Scm-1 with 68% of water uptakes. The obtained results could reflect the enhance performance of mPTA-Si membrane and high potential alternative membrane for DMFC. Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR) results proved a good dispersion and the existence of Keggin anion from mPTA-Si particles formed a strong interfacial bonding between fillers and PVA matrix. Owing to these superior characteristics of the mPTA-Si, PVA/ mPTA-Si membrane is considerably promising materials as PEM for DMFC application.