Piezoelectric materials have advantages of fine-tuning photocatalytic performance through harvesting mechanical energy and open a new avenue in facilitating green catalytic reaction. Herein, polyvinylidene fluoride (PVDF), a flexible piezoelectric material, was introduced to synthesize a novel Cd0.9Zn0.1S-ZnO@C/PVDF (CZS-ZO@C/PVDF) piezo-photocatalytic film by spin coating and immersion phase conversion method. Benefiting from the piezoelectricity of PVDF and the internal electric field (IEF) of CZS-ZO@C Step-scheme (S-Scheme) heterojunction, CZS-ZO@C/PVDF was able to induce a hydrogen generation rate of 34.9 mmol g−1 h−1 activated by ultrasound and visible light (U-L), which is ∼17.5 times of Cd0.9Zn0.1S/PVDF (CZS/PVDF) and ∼7.4 times of the photocatalysis rate activated by visible light only (L). Piezoelectric measurements and COMSOL simulation illustrated the excellent piezoelectricity of CZS-ZO@C/PVDF film, which exhibits a piezoelectric coefficient (d33) of 9.9 pm V−1 and a piezoelectric potential of 874 mV (under 0.5 MPa). The reaction mechanism for the exceptional piezo-photocatalytic performance was finally disclosed through density functional theory (DFT) calculation and electrochemical tests. This study enriches the application scope of piezoelectric materials in sustainable energy catalysis and provides a new direction to develop efficient piezoelectric photocatalysts.