A series of composite anion exchange membranes was synthesized via in-situ copolymerization of various ratios N-vinyl formamide (NVF) and divinylbenzene (DVB), supported by porous polytetrafluoroethylene (PTFE) polymer matrix, and followed by alkaline hydrolysis, and quaternization of the composite membranes with epoxypropyltrimethylammonium chloride (EPTMAC). FTIR and SEM analyses revealed that the composite membranes were successfully prepared. Moreover, the hydrophilic property of the composite membrane improved by introduction of the quaternized poly(NVF-co-DVB) copolymer. Water uptake, swelling ratio, and conductivity showed upward trends by increase of NVF amount. The copolymer with 95% of NVF showed the highest elongation at break (102%, room temperature) and conductivity (5.15 × 10 −2 S/cm, 80 C). After immersion of the PNDB 95%-N membrane in 5 mol/L NaOH solution for 96 h at room temperature, the conductivity (60 C) of the membrane decreased to 3.99 × 10 −2 S/cm. Moreover, the membrane registered weight loss under 4.5%, caused by degradation of the quaternary ammonium groups in NaOH solution. All in all, in 3 mol/L methanol solutions, the composite membranes showed permeability ranging from 7.6% to 19.7%, if compared to the Nafion ®-115 membrane, showing good alcohol resistance.