Herein, we introduced the fully polysaccharide-based membranes as self-standing, solid polyelectrolytes for anion exchange membrane fuel cell (AEMFC) application. To this end, cellulose nanofibrils CNFs have been successfully modified by organosilane reagent, yielding the quaterized-CNFs (CNF (D)) as evidenced by FTIR, 13C NMR, TGA/DSC and ζ potential measurement. Both, neat (CNF) and CNF(D) particles were introduced in situ to the chitosan (CS) membrane during the solvent casting process, resulting in a composite membrane, comprehensively evaluated in terms of morphology, KOH uptake and swelling ration, EtOH permeability, mechanical properties, ionic conductivity and cell performance. The results indicate on higher Young’s modulus (119%), tensile strength (91%), ion exchange capacity (177%), ionic conductivity (33%) of CS-based membranes in comparison to the commercial Fumatech FAA-3-50 membrane. The addition of CNF filler improved the thermal stability of CS membranes and decreased the total mass loss. CNF (D) filler offers the lowest (4.23 10-5 cm2 s-1) EtOH permeability to respective membrane, which is in the same range as the commercial type (3.47 10-5cm2s-1). The most significant (~ 78%) improvement in power density at 80 °C is observed for the CS membrane with neat CNF compared to the commercial Fumatech FAA-3-50 membrane (62.4 mW cm-2 vs 35.1 mW cm-2). The fuel cell tests have shown that all CS-based AEMs exhibited higher maximum power densities than the commercial type AEM at 25 °C and 60 °C with humidified or un-humidified oxygen, demonstrating their potential in low-temperature DEFC applications.