Smart energy harvesting through the surrounding environment generates sufficient energy to drive the low-power consumption systems. It is the forthcoming revolution in smart (or self-powered) technology and results in abolishing the usage of complex batteries, external circuit components, and natural sources. To date, extensive fabrication methods, the growth of ZnO nanostructures on plastic substrates, and flexible piezoelectric polymer film-based devices were tested to improve the performance of piezoelectric nanogenerator (PNG) as a prominent energy-harnessing approach for the development of sustainable independent power sources. Still, PNG technology suffers from brittleness, leakage current issues, high electrical output generation, and long-term durability, which can be possible to control by the composite technology, that is, polymer/nanoparticles. The objective of this book chapter determines the rapid growth of multifunctional, flexible composite structures through various methods (e.g., ionotropic gelation method, groove technique, ultrasonication followed by solution-casting methods) for high output energy generation and self-powered sensor/system studies.