Introducing piezoelectric materials with the built-in electric field caused by mechanical force has been confirmed as an effective strategy to boost the separation efficiency of photoexcited charge carriers that determines the photocatalytic performance. In this study, we introduced Bi4Ti3O12 with superior piezoelectric properties into BiVO4-Bi4V2O10 materials to synthesize a 2D Bi4Ti3O12-BiVO4-Bi4V2O10 photocatalyst via a facile hydrothermal method. Compared with bare BiVO4, the Bi4Ti3O12-BiVO4-Bi4V2O10 piezo-photocatalytic activity towards Cr(VI) removal and oxygen evolution is boosted remarkably under both illumination and ultrasound treatments. The promoted photocatalytic activity can be ascribed to the accelerated photoexcited carrier separation efficiency driven by the polarization electric field and the synergy effect in the heterostructure. This work provides a simple and sustainable strategy for the design and development of piezo-photocatalysts with high photoredox activity capacity.