The present paper describes a preparation method and molecular investigations of new biodegradable proton-conducting carbohydrate polymer films based on alginic acid and benzimidazole. Electric conductivity was studied in a wide temperature range in order to check the potential application of these compounds as membranes for electrochemical devices. Compared to pure alginic acid powder or its film, the biodegradable film of alginic acid with an addition of benzimidazole exhibits considerably higher conductivity in the range above water boiling temperature (up to approximately 10 −3 S/cm at 473K). Due to this important feature the obtained films can be considered as candidates for application in high-temperature electrochemical devices. The microscopic nature and mechanism of the conduction in alginate based materials were studied by proton nuclear magnetic resonance (NMR). The results show specific changes in morphology and molecular dynamics between pure alginate powders and the films obtained without and with the addition of benzimidazole molecules.