In this work, composite films of molybdenum disulfide (MoS2) with poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) were fabricated using aqueous phase transformation and hydrothermal methods, aiming at efficiently degrading tetracycline hydrochloride (TC). The findings revealed that the degradation efficiency of TC by MoS2@PVDF-HFP, when subjected to a combined photocatalysis process involving a simulated pressure electric field and aeration, reached a remarkable 96.11% within 1 hour-surpassing the performance observed under individual conditions. The changes in the electron density cloud on the films surface induced by the pressure electric field and the acceleration of electron transfer rate between contact interfaces were evident. Notably, the composite films exhibited a stable performance with a TC removal rate of 90.23% after five cycles, including a relatively stable degree of mineralization. We employed Density Functional Theory (DFT) to investigate the changes in the state density of MoS2@PVDF-HFP under different conditions, such as compressive stress, tension, and no force. This further clarified the mechanism of piezoelectric coupling photocatalysis promoting induced charge transfer on the films surface. The research findings presented in this paper provide a promising avenue for the application of piezoelectric field-assisted photocatalysis in enhancing material performance.