Molybdenum disulfide (MoS2) is a promising piezoelectric catalytic material that has garnered extensive research attention. However, its application is hindered by its inherent centrosymmetric structure, leading to comparatively low piezoelectric efficiency. To address this issue, this study proposed a dual-defect (sulfur vacancies and boron-loaded) construction strategy to break the central symmetry of MoS2, and a series of Vs-B/MoS2 catalysts with ultrahigh piezoelectric catalytic efficiency were successfully prepared. The optimized Vs-B3.0/MoS2 catalyst exhibited exceptional piezoelectric catalytic activity, with a piezoelectric force microscopy (PFM) piezoelectric response amplitude of 403.9 pm and a piezoelectric coefficient of 35.1 pC N−1, which is 3.85 and 6.27 times higher than those of Vs-MoS2, respectively. Electrochemical tests and density functional theory calculations indicated that the enhanced piezoelectric performance can be attributed to boron doping and sulfur vacancy formation. These structural defects facilitate charge separation and increase material conductivity, significantly boosting piezoelectric properties. Within 60 min, the Vs-B3.0/MoS2 catalyst efficiently degraded 92.6 % of tetracycline. The electron paramagnetic resonance (EPR) characterization showed that ·OH and ·O2− were the main active radicals of the piezoelectric catalysis. In addition, the material exhibits significant bactericidal properties against E. coli. This study offers novel methods and technological support to enhance the piezoelectric properties of transition metal sulfides and efficiently purify water pollutants.