PVDF + WS₂ fibers were fabricated via an electrospinning method and utilised as sample materials to explore the effect of structure on catalytic activity. It is discovered that the electrospun PVDF + WS₂ composite has superior piezocatalytic and photocatalytic properties compared to PVDF. This can be attributed to the increased spontaneous polarisation caused by the ferroelectric PVDF contact, which is also supported by piezo force microscopy (PFM) analysis. Piezocatalysis was examined under ultrasonication as well as under low-frequency vibrations. When membranes were subjected to low-frequency vibrations, the composite membrane was able to degrade 44% MB dye (2.5 mg L⁻¹) in 240 min, making it a viable candidate for the removal of contaminants. Furthermore, the by-product of the photo-piezo degraded dye was studied for phytotoxicity assessment using Vigna radiata seeds. In addition, the composite membrane photocatalytically eliminated more than 99% of Escherichia coli and Staphylococcus aureus bacteria within 120 min of visible light exposure. We propose that this work offers mechanistic insights into the role of phase structures towards catalytic performance and an innovative strategy for developing environmentally friendly catalysts capable of efficiently utilising different energy sources.