Bisphenol A (BPA) has raised worldwide concern owing to its ecological risks, highlighting the urgent need to develop efficient removal strategies in wastewater treatment. Ametal–organic framework (Bio-MOF-1) piezoelectrically activating peroxymonosulfate (PMS) process (Bio-MOF-1/PMS/US) was developed to remove BPA at 98.5%, which was 3.5 times higher than the Bio-MOF-1/US process. Further analysis confirmed that the piezoelectric field initiated by Bio-MOF-1 could reduce the activation energy of PMS and then promote the reaction of PMS with holes and electrons to convert into 1O2 and OH. The steady-state concentration of 1O2 was 4 orders of magnitude higher than OH, indicating the dominant contribution of 1O2 for BPA removal, which resulted in the efficient BPA removal from a variety of anions, organics, and municipal wastewater through a low-risk manner. This work provides new perspectives for the application of MOF-based materials in the field of piezoelectric catalysis and promising applications in wastewater remediation.