Broader contextDirect methanol fuel cells (DMFCs) have reached a high level of development and are now almost universally referred to as the sixth-fuel-cell type. In terms of applications, they are set to function as power sources for a range of mobile applications, a situation brought about by the convenience of storage of liquid fuel. For an expansion of the applications of DMFCs, efforts are being expended to develop improved and cost-effective polymer-electrolyte membranes that would mitigate methanol cross-over from the anode to the cathode. It is desirable that these membranes comprise non-hazardous chemicals. Accordingly, this study is an attempt to realise a membrane electrolyte from natural precursors such that the process generates little toxicity to the environment. The polymer electrolyte membrane, derived from naturally abundant chitosan (CS) and hydroxy ethyl cellulose (HEC), possesses good methanol-barrier properties and exhibits high proton-conductivity, the pre-requisites required for a membrane to be used in DMFCs. Stabilised salt of phosphotungstic acid (PTA) is incorporated to the CS-HEC blend to enhance the proton conductivity of the membrane. Preferential water-sorption characteristics of the CS-HEC-PTA mixed matrix play an important role in ameliorating the DMFC performance.