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The development of cheap and efficient proton conducting polymers attracts scientists' attention, resulting in its potential role in fuel cell applications. This work synthesized a novel cellulose acetate-g-poly(sodium 4-styrene sulfonate) via free radical polymerization using potassium persulfate (KPS) as an initiator. The effects of varying KPS concentration, cellulose acetate (CA), sodium 4-styrene sulfonate (Na-SSA) content, reaction time, and temperature on the grafting parameters were studied. Grafting parameters, including the grafting yield (GY %), Add-on (%) and grafting efficiency (GE %) of the grafting reaction, were evaluated. Additionally, FTIR, TGA, DSC, 1HNMR and EDX analyses were studied. The developed graft copolymers membranes illustrated increased water uptake values and ion exchange capacity (IEC) with the add-on (%). Furthermore, the proton conductivity of the developed graft copolymers was found superior (4.77 × 10−3 S.cm−1) to the pristine CA membrane (0.035 × 10−3 S.cm−1). [ABSTRACT FROM AUTHOR]