In this study, we integrate plasmonic metal nanomaterials with a piezoelectric polyvinylidene fluoride (PVDF) polymer and lithium niobate (LiNbO3) based composite to form an all-solid-state flexible self-energized sensor. We demonstrate that following the application of a load, the film enhances the surface-enhanced Raman spectroscopy (SERS) signal of an analyte molecule up to 14 times. The piezoelectric β-phase of PVDF in the film is optimized through the introduction of multi-walled carbon nanotubes and post-fabrication UV irradiation annealing. Additionally, the SERS signal enhancement can be further increased by the application of in situ UV light irradiation of the sample, resulting in the generation of photoexcited electrons from LiNbO3 microparticles introduced into the composite. Both the application of a mechanical displacement and the UV light-induced charge generation result in an improved charge transfer between the film and an analyte molecule. The piezoelectric PVDF/LiNbO3 film has been shown to be a suitable SERS platform for the detection of important biological molecules, demonstrating the potential of the substrate for fast on-site detection applications.