Electrochemical power tools are regarded as essential keys in a world that is becoming increasingly reliant on fossil fuels in order to meet the challenges of rapidly depleting fossil fuel supplies. Additionally, due to the industrialization of societies and the growth of diseases, the need for sensitive, reliable, inexpensive, and portable sensors and biosensors for noninvasive monitoring of human health and environmental pollution is felt more than ever before. In recent decades, electrospun fibers have emerged as promising candidates for the fabrication of highly efficient electrochemical devices, such as actuators, batteries, fuel cells, supercapacitors, and biosensors. Meanwhile, the use of synthetic polymers in the fabrication of versatile electrochemical devices has raised environmental concerns, leading to an increase in the quest for natural polymers. Natural polymers are primarily derived from microorganisms and plants. Despite the challenges of processing bio-based electrospun fibers, employing natural nanofibers in the fabrication of electrochemical devices has garnered tremendous attention in recent years. Here, various natural polymers and the strategies employed to fabricate various electrospun biopolymers are briefly covered. The recent advances and research strategies used to apply the bio-based electrospun membranes in different electrochemical devices are carefully summarized, along with the scopes in various advanced technologies. A comprehensive and critical discussion about the use of biopolymer-based electrospun fibers as the potential alternative to non-renewable ones in future technologies is briefly highlighted. This review will serve as a field opening platform for using different biopolymer-based electrospun fibers to advance the electrochemical device-based renewable and sustainable technologies, which will be of high interest to a large community. Accordingly, future studies should focus on feasible and cost-effective extraction of biopolymers from natural resources as well as fabrication of high-performance nanofibrous biopolymer-based components applicable in various electrochemical devices.