Poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) due to its outstanding electrochemical properties has been known as a potent candidate for a wide spectrum of applications. Herein, taking advantage of its water-soluble nature, we attuned a novel corrosion inhibitor based on PEDOT:PSS and Zn2+ for the fabrication of self-healing silane-based corrosion protective coatings. To this aim, we chelated PEDOT:PSS chains with Zn2+ cations to synthesis the organic-metallic pigments, and then the prepared pigments were incorporated into a silane-based coating. In the first step, the structural features of the pigment were well-studied by Fourier transform infrared spectroscopy (FTIR), Ultraviolet-visible (UV-Vis), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) techniques before and after chelation. Afterwards, the corrosion protection ability of the prepared pigments in solution and coating phases were evaluated using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. The attained results validated that the incorporation of chelated PEDOT:PSS-Zn2+ pigments into the matrix of silane-based coatings resulted in excellent self-healing corrosion protection performance. Further morphological and structural characterization confirmed the formation of a corrosion protective passive layer on the surface of metallic substrates and the scratched regions of coatings.