In this study, the pyridinium anion exchange precursor was prepared by alkylation of 4-bromomethyl benzoic acid to pyridine and then the corresponding covalently cross-linked pyridinium based AEMs were obtained by esterification reaction through the prepared pyridinium salt and polyvinyl alcohol (PVA) as a base material in presence of tetraethoxysilane (TEOS) as a crosslinker. The prepared anion exchange membranes are characterized by FTIR, SEM, TGA and DMA. Td values are in the range of 322–335°C. The tensile strength (TS) ranges from 43.74 to 47.23MPa and elongation at break (Eb) in the range of 262.59–474.44%. The acid dialysis coefficients (UH) are in the range of 1.28–1.88×10−2m/h, greater than the well known commercial membrane DF-120 (9×10−3m/h). The membrane containing 40wt% of PVA has the highest separation factor (S) of 71.35. Note that the DD tests have been evaluated according to the membrane structure and its composition.