A polymer composite was prepared by incorporating 5-20 wt% quaternized chitosan (Q-chitosan) nanoparticles into quaternized polyvinyl alcohol (Q-PVA) to enhance the dimensional stability and conductive properties. Compared with the pristine Q-PVA membrane, the ionic conductivity of the QPVA composites with 5-10 wt% Q-chitosan was improved due to increased polymeric free volume hole density. The methanol permeability is suppressed in these Q-PVA/Q-chitosan composites because of the confined swelling in the presence of the fillers, shrinking the free volume size. The Q-PVA/5% Q-chitosan composite exhibits higher peak power density (Pmax) than other Q-PVA membranes in direct methanol fuel cells. A Pmax of 92 mW cm(-2) is attained using the Q-PVA/5% Q-chitosan composite at 90 degrees C with 5 -6 mg cm(-2) catalyst loads on micro-porous layer-containing carbon cloth. The high load of 20 wt% Qchitosan does not benefit ionic conduction and power generation, probably due to interfacial resistance at rough surfaces. Using the Q-PVA/5% Q-chitosan composite and reduced catalyst loads of 1-2 mg cm(-2) on pristine carbon cloth, Pmax of 90mWcm(-2) can be achieved at 60 degrees C for both methanol and ethanol fuel cells, but declined at 90 degrees C due to insufficient catalysts. Overall the Q-PVA/Q-chitosan composite offers a potential electrolyte for energy devices operating in an alkaline environment. (C) 2018 Elsevier Ltd. All rights reserved.