Polyvinyl alcohol (PVA) and potassium hydroxide (KOH) have been used to prepare alkaline solid polymer electrolytes (ASPE) films. The films were stored in a dry environment for 30 and 100 days. The highest room temperature conductivity for the PVA:KOH film with weight percentage ratio of 1:0.67 during storage for 30 and 100 days were (8.5±0.2)×10⁻⁴ and (1.3±0.1)×10⁻⁷ S cm⁻¹, respectively. The conductivity–temperature behaviour after 30 and 100 days of storage of the alkaline polymer electrolytes is Arrhenian and liquid-like. The structural, morphological and thermal studies of the ASPE films are also presented in this paper.