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Electrical, thermal and mechanical studies were carried out on proton conducting electrolytes, based on poly(vinylpyrrolidone) (PVP) with ammonium perchlorate (NH4ClO4). Considering both the conductivity and manageability of films, the optimal PVP and NH4ClO4 weight ratio was 7:3 with 15 wt% water, exhibiting a protonic conductivity of 0.91×10-44 Scm-1 at 30 oC and 1.12×10-2 Scm-1 at 80 oC. Thermal studies showed that the crystallites of excess NH4ClO4 were formed inside the electrolyte, but they were decreased significantly with increasing water content. Cellulose was mixed to improve the mechanical strength of the hydrated samples. In a reinforced matrix of PVP/Cellulose complexes, the water retention property was improved significantly, thus exhibiting a slower decrease in conductivity over time.