The methods available for the disposal of synthetic polymers are not advanced in an environment-friendly way. Consequently, their waste persists as a non-degradable pollutant that discharges toxic substances, which have now reached the deepest parts of the ocean. As an alternative, biopolymers such as polylactic acid, polyhydroxyalkanoates, and poly(butylene succinate), synthesized from natural sources such as plants, animals, and microbes, are an eco-friendly option, as they are biodegradable and a better option to shift from synthetic polymer dependency. The fabrication of electrospun nanofibers (NFs) using biopolymers is a novel approach, by which new ideas have been proposed in various fields, such as agriculture, biomedical, food packing, textiles, adsorption, drug delivery, three-dimensional printing, etc. Electrospun NFs are receiving increasing attention due to their diverse properties, including flexibility. This review provides a perception of the novel biopolymers that are currently utilized by the electrospun technique and their various applications.