Bi4Ti3O12 (BiTO) is a typical bismuth-layered Aurivillius ferroelectric material for its potential application in photocatalysis. In this study, Au/BiTO hybrid was fabricated by precipitating Au nanoparticles onto BiTO nanoflake using a sodium citrate reduction route. This integration has led to a remarkable enhancement in the photocatalytic efficiency, which is attributed to the synergistic coupling of piezoelectric effect of BiTO with the localized surface plasmon resonance (LSPR) of Au nanoparticles. The incorporation of Au nanoparticles onto the BiTO matrix has significantly boosted the light absorption and charge carrier separation, thereby augmenting the photocatalytic activity. Notably, Au/BiTO-2 composite exhibits exceptional photocatalytic performance, demonstrating the complete degradation of RhB within 40 min under full-spectrum light irradiation. Moreover, Au/BiTO-2 displays a robust photocatalytic action against other organic pollutants, including methyl orange (MO), ofloxacin (OFLX) and tetracycline hydrochloride (TC). Further enhancement of photocatalytic process is achieved when combing light irradiation with ultrasonic excitation. The ultrasonic waves break the static spontaneous polarization through alternating piezoelectric potential, which accelerates the catalytic reaction. The photocatalytic action rate of Au/BiTO-2 toward RhB reaches a value as high as 0.0984 min−1, which is nearly 2.3 folds increasement compared to that of pristine BiTO. The possible synergistic mechanism caused by piezoelectric effect and exciton-plasmon effect is discussed in detail. The work not only enriches our understanding of the underlying principles but also supply a new strategy to design high-performance catalysts in the field of environmental remediation and energy conversion.