Piezoelectric polymers are a class of material that belong to carbon–hydrogen-based organic materials with a long polymer chain. They fill the void where single crystals and ceramics fail to perform. This characteristic of piezoelectric polymers made them unique. Their piezoelectric stress constant is higher than ceramics and the piezoelectric strain is lower compared to ceramics. This study’s goal is to present the most recent information on poly(vinylidene fluoride) with trifluoroethylene P(VDF-TrFE), a major copolymer of poly(vinylidene fluoride) PVDF with piezoelectric, pyroelectric, and ferroelectric characteristics. The fabrication of P(VDF-TrFE) composites and their usage in a variety of applications, including in actuators, transducers, generators, and energy harvesting, are the primary topics of this work. The report provides an analysis of how the addition of fillers improves some of the features of P(VDF-TrFE). Commonly utilized polymer composite preparation techniques, including spinning, Langmuir–Blodgett (LB), solution casting, melt extrusion, and electrospinning are described, along with their effects on the pertinent characteristics of the polymer composite. A brief discussion on the literature related to different applications (such as bio-electronic devices, sensors and high energy-density piezoelectric generators, low mechanical damping, and easy voltage rectifiers of the polymer composite is also presented.