Energy harvesting exploits ambient sources of energy such as mechanical loads, vibrations, human motion, waste heat, light or chemical sources and converts them into useful electrical energy. The applications for energy harvesting include low power electronics or wireless sensing at relatively lower power levels (nW to mW) with an aim to reduce a reliance on batteries or electrical power via cables and realise fully autonomous and self-powered systems. This review focuses on flexible energy harvesting system based on polyvinylidene fluoride based polymers, with an emphasis on manipulating and optimising the properties and performance of the polymeric materials and related nanocomposites through structuring the material at multiple scales. Ferroelectric properties are described and the potential of using the polarisation of the materials for vibration and thermal harvesting using piezo- and pyro-electric effects are explained. Approaches to tailor the ferroelectric, piezoelectric and pyroelectric properties of polymer materials are explored in detail; these include the influence of polymer processing conditions, heat treatment, nanoconfinement, blending, forming nanocomposites and electrospinning. Finally, examples of flexible harvesting devices that utilise the optimised ferroelectric polymer or nanocomposite systems are described and potential applications and future directions of research explored.