The Seebeck effect in unipolar ion-conducting, solid-state polymers is characterized. The high Seebeck coefficient and sign in polymer ion conductors is explained via analysis of thermogalvanic multicomponent transport. A solid-state, water-processeable, flexible device based on these materials is demonstrated, showcasing the promise of polymers as thermogalvanic materials. Thermogalvanic materials based on ion-conducting polymer membranes show great promise in the harvesting of waste heat.