Ferroelectrics, which generate a switchable electric field across the solid–liquid interface, may provide a platform to control chemical reactions (physical properties) using physical fields (chemical stimuli). However, it is challenging to in-situ control such polarization-induced interfacial chemical structure and electric field. Here, we report that construction of chemical bonds at the surface of ferroelectric BiFeO3 in aqueous solution leads to a reversible bulk polarization switching. Combining piezoresponse (electrostatic) force microscopy, X-ray photoelectron spectroscopy, scanning transmission electron microscopy, first-principles calculations and phase-field simulations, we discover that the reversible polarization switching is ascribed to the sufficient formation of polarization-selective chemical bonds at its surface, which decreases the interfacial chemical energy. Therefore, the bulk electrostatic energy can be effectively tuned by H+/OH− concentration. This water-induced ferroelectric switching allows us to construct large-scale type-printing of polarization using green energy and opens up new opportunities for sensing, high-efficient catalysis, and data storage.