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Polyvinylidene fluoride (PVDF) polymer films, renowned for their exceptional piezoelectric, pyroelectric, and ferroelectric properties, offer a versatile platform for the development of cutting-edge micro-scale functional devices, enabling innovative applications ranging from energy harvesting and sensing to medical diagnostics and actuation. This paper presents an in-depth review of the material properties, fabrication methodologies, and characterization of PVDF films. Initially, a comprehensive description of the physical, mechanical, chemical, thermal, electrical, and electromechanical properties is provided. The unique combination of piezoelectric, pyroelectric, and ferroelectric properties, coupled with its excellent chemical resistance and mechanical strength, makes PVDF a highly valuable material for a wide range of applications. Subsequently, the fabrication techniques, phase transitions and their achievement methods, and copolymerization and composites employed to improve and optimize the PVDF properties were elaborated. Enhancing the phase transition in PVDF films, especially promoting the high-performance β-phase, can be achieved through various processing techniques, leading to significantly enhanced piezoelectric and pyroelectric properties, which are essential for diverse applications. This concludes the discussion of PVDF material characterization and its associated techniques for thermal, crystal structure, mechanical, electrical, ferroelectric, piezoelectric, electromechanical, and pyroelectric properties, which provide crucial insights into the material properties of PVDF films, directly impacting their performance in applications. By understanding these aspects, researchers and engineers can gain valuable insights into optimizing PVDF-based devices for various applications, including energy-harvesting, sensing, and biomedical devices, thereby driving advancements in these fields.