With the continuing efforts to explore alternatives to petrochemical-based polymers and the escalating demand to minimize environmental impact, bio-based polymers have gained a massive amount of attention over the last few decades. The potential uses of these bio-based polymers are varied, from household goods to high end and advanced applications. To some extent, they can solve the depletion and sustainability issues of conventional polymers. As such, this article reviews the trends and developments of bio-based polymers for the preparation of polymer electrolytes that are intended for use in electrochemical device applications. A range of bio-based polymers are presented by focusing on the source, the general method of preparation, and the properties of the polymer electrolyte system, specifically with reference to the ionic conductivity. Some major applications of bio-based polymer electrolytes are discussed. This review examines the past studies and future prospects of these materials in the polymer electrolyte field.