Abstract The main objectives of the present work are the study of the compositions from starch or modified (carboxymethylated) starch (CMS) with polyvinyl alcohol (PVA) to develop films containing decamethoxine as transdermal therapeutic systems. The influence of the content of CMC in compositions with PVA and in films prepared from the compositions on their properties are investigated. The effect of the antiseptic drug decamethoxine on changes in the properties of films has been investigated. It is established that the compositions of polymers had a high degree of thixotropic recovery in contrast to their individual components. According to the Zellinger–Heidingsfeld criterion the polymers are incompatible for PVA/CMS compositions at mass ratios of 75:25. The content of decamethoxine in the films increases their sorption properties from 2% to 7% depending on the humidity of the medium. A stable release of decamethoxine from the PVA/СMS polymer film with ratios of 75:25 and 50:50 is observed. Microbiological studies of films based on PVA/CMS mixtures show no growth of fungi on the films. The results reveal the possibility of developing a polymer system by the solution‐casting method to develop films based on modified starch, PVA, and drugs for the manufacturing of effective pharmaceuticals.