Electrospinning method was optimized for fabrication of functional and mechanically strong nanofiber mats by reinforcement of Nafion resin into polymer polyacrylonitrile (PAN). Nafion and PAN were blended by the sol–gel method using the solvents N,N-dimethylacetamide (DMAc) and N,N-dimethylformamide (DMF). Fabricated membranes were characterized by their geometrical, physicochemical and mechanical properties. The study revealed that, nanofibers of 450–80 nm diameter were fabricated. The Nafion–PAN composite nanofiber exhibited more stability and better mechanical properties due to reinforcement of Nafion into PAN matrices. These composite nanofiber mats exhibited the ultimate tensile strength (UTS) of 376 and 286 kPa as compared to UTS of 157 kPa for neat PAN nanofibers. Nanofiber membranes also possessed adsorption properties showing an adsorption removal affinity for Cr³⁺ metal ions up to approximately 45%. Electrospun nanofiber mats also exhibited high surface area and can have multifaceted applications.