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[Display omitted] • The piezoelectric properties of the PVDF has been improved by incorporating Bi 2 ZnB 2 O 7 via electrospinning method. • Electrospun nanofibers exhibit high mechanical strength and a favourable nanoconfinement effect on interfaces, which promotes the synergistic piezo-phototronic effect in piezoelectric heterostructures. • Achieved 74% degradation with a kinetic rate of 7.3 × 10−3 min−1 of methylene blue under combined effect of visible light irradiation and ultrasonication. • The mechanism underlying piezo-photocatalytic dye degradation has been explained with scavenger test. To enhance the piezoelectric capabilities of the β-phase of poly(vinylidene fluoride), a new composite membrane was prepared via electrospinning. This consist of Bi 2 ZnB 2 O 7 and poly(vinylidene fluoride). A comparison of electrospun and composite fibers showed a significant increase in β-phase content. XRD and FTIR were used to characterize the samples' structures. FE-SEM and HR-TEM were also used to examine sample morphology. The optical properties of the BBZO-PVDF membrane were further assessed using UV–visible diffuse reflectance spectroscopy. The composite membrane's effectiveness was tested using photocatalysis, piezocatalysis, and photo-piezocatalysis. Methylene blue (MB) dye was degraded by these methods. The synergy between light and piezoelectric actions improved degradation performance significantly. It achieved a 74% degrading efficiency and a kinetic rate constant of 7.3 × 10−3 min−1. The findings show that the BBZO-PVDF composite membrane has great potential for enhanced environmental remediation and catalytic processes. [ABSTRACT FROM AUTHOR]