AbstractIn this study, trimercapto‐S‐triazine trisodium salt (TMT) with threefold rotational symmetry as a corrosion inhibitor was introduced into 2 mol ⋅ L−1 ZnSO4 medium. By electrochemical measurements, the corrosion inhibition efficiency of the zinc electrodes was 92.52 % when the concentration of TMT corrosion inhibitor was 2 mmol ⋅ L−1. Based on the microstructural characterization and theoretical analysis of Zn electrodes, it was confirmed that S and N atoms of TMT corrosion inhibitor serve as alternately zinc‐philic adsorption sites with sixfold rotational symmetry for the formation of intermolecular complexes. Adsorption energies of TMT on Zn surfaces were calculated and indicated that the bonds of Zn−N and Zn−S promoted anchoring adsorption on sixfold symmetric (002) plane of zinc. Meanwhile, TMT corrosion inhibitor can adsorb Zn2+ from the electrolyte and directionally deposit them on the surface of Zn (002), effectively avoiding the occurrence of dendrites. This study changes the common knowledge that organic corrosion inhibitors must form hydrophobic films to have corrosion inhibition performance, and provides a new approach for using small organic molecules with anchoring adsorption as metal corrosion inhibitors.