Simplified and flexible fabrication methods, high output performance, and extreme flexibility of polymer-based nanocomposites represent versatile designs in self-powering devices for wearable electronics, sensors, and smart societies. Examples include polyvinylidene fluoride and its copolymers-based piezoelectric nanogenerators, green and recyclable triboelectric nanogenerators, etc. Advanced functionalities, multi-functional properties, and the extensive lifetime required for nanogenerators inspire researchers to focus on structural modifications of the polymeric materials, to fully exploit their performances. Phase separation is a physicochemical process in which polymeric phases rearrange, resulting in specific structures and properties, that ultimately influence mechanical, electronic, and other functional properties. This article will study the phase separation strategies used to modify the polymeric base, both physically and chemically, to generate the maximum electric power upon mechanical and frictional deformation. The effect of interfacial modification on the efficiency of the nanogenerators, chemical and mechanical stability, structural integrity, durable performance, and morphological appearance will be extensively covered in this review. Moreover, piezo- and triboelectric power generation have numerous challenges, such as poor resistance to mechanical deformation, reduced cyclic performance stability, and a high cost of production. These often depend on the method of developing the nanogenerators, and phase separation provides a unique advantage in reducing them. The current review provides a one-stop solution to understand and disseminate the phase separation process, types and mechanisms, advantages, and role in improving the piezoelectric and triboelectric performances of the nanogenerators.