A novel blend of membranes made of Nafion^® and poly(vinyl pyrrolidone) (PVP) was prepared and characterized to investigate its applicability in proton exchange membrane fuel cells (PEMFCs). In addition to being effectively proton conductive, the membranes exhibited better mechanical strength, chemical stability and adequate water retention ability as well as ion exchange capacity comparable to that of cast Nafion^® membrane. The data obtained from an electrochemical impedance spectroscopy (EIS) fitting of the fuel cells revealed the membrane electrode assemblies (MEAs) made of 0.5 wt. % PVP/ Nafion^® had lower ohmic and charge transfer resistance compared to that of Nafion^® membrane. The intermolecular interactions and morphology of these membranes were assessed using Fourier-transform infrared spectroscopy and field-emission scanning electron microscopy. The results of the performance curve indicate that the introduction of PVP as a modifier played a vital role in improving the membrane performance. Accordingly, this solution casted polymer electrolyte membrane with suitable PVP content offers a simple way to improve electrochemical, mechanical and chemical properties and thereby promises the prospect for use in low-temperature PEMFCs.