Electroactive polymers (EAPs), a new class of materials, have the potential to be used for applications like biosensors, environmentally sensitive membranes, artificial muscles, actuators, corrosion protection, electronic shielding, visual displays, solar materials, and components in high-energy batteries. The commercialization of synthetic EAPs, however, has so far been severely limited. Biological polymers offer a degree of functionality not available in most synthetic EAPs. Carbohydrate polymers are produced with great frequency in nature. Starch, cellulose, and chitin are some of the most abundant natural polymers on earth. Biopolymers are a renewable resource and have a wide range of uses in nature, functioning as energy storage, transport, signaling, and structural components. In general, electroactive materials with polysaccharide matrices reach conductance levels comparable with synthetic ion-conducting EAPs. This review gives a brief history of EAPs, including terminology, describes evaluation methods, and reports on the current progress of incorporating polysaccharides as matrices for doped, blended, and grafted electroactive materials.