The main obstacle of high-performance cationic functionalization chitosan (CS) as anion exchange membranes (AEMs) is the trade-off between mechanical stability and ionic conductivity. Here, in-situ ionic crosslinking between the deprotonated hydroxyl group and quaternary ammonium group under alkaline conditions was ingeniously applied to improve the mechanical stability of highly quaternized CS (HQCS) with high IEC (>2 mmol g−1). Meanwhile, to further reduce the swelling and enhance the hydroxide conductivity, a mechanically robust hydroxide ion conduction network, quaternized electrospun poly(vinylidene fluoride) (QPVDF) nanofiber, was subsequently used as the filling substrate of in-situ crosslinked HQCS to prepare dual reinforced thin AEMs. The introduction of a robust QPVDF nanofiber mat can not only greatly improve the mechanical properties and limit swelling, but also create facile ion transport channels. Notably, the HQCS/QPVDF-74.0 composite membrane demonstrates perfect dimensional stability, high mechanical performance and excellent alkaline stability, as well as superior ionic conductivity of 66.2 mS cm−1 at 80 °C. The thus assembled alkaline direct methanol fuel cell displays a maximum power density of 132.30 mW cm−2 using 5 M KOH and 3 M methanol as fuels at 80 °C with satisfactory durability.