Silane (sol-gel)-based coatings have been introduced as an eco-friendly system for reducing the metals' corrosion in NaCl solutions. However, due to the lack of active protection property for this type of coatings, their modification is totally recommended for achieving durable protection properties. The present study introduces Beta-cyclodextrin (β-CD) as a novel/effective organic nano-container for Benzimidazole (BM) encapsulation to obtain reliable active protection property via a controlled-release property.The chemical structure of the β-CD-BM macromolecule was explored by Fourier-transform infrared spectroscopy (FT-IR), X-Ray diffraction (XRD), and Ultraviolet-visible spectroscopy (UV-Vis). Besides, the Electrochemical Impedance Spectroscopy (EIS) and polarization (potentiodynamic) tests were carried out for investigating the inhibition impacts of the constructed containers. The exposed and unexposed samples' surfaces were analyzed by Field Emission Scanning Electron Microscope (FE-SEM), Energy Dispersive Spectroscopy (EDS)/mapping, and Grazing incidence X-ray diffraction (GIXRD) experiments. Also, the EIS test was conducted over the Silane-based composite film (SCF) for analyzing the anti-corrosion performance of the constructed composites.The EIS achievements demonstrated that by the addition of β-CD-BM complexes to the saline solution, the mild steel corrosion was mitigated by about 84%. The EIS results also displayed that the total resistance of the modified composite was enhanced from 5540 Ω.cm2 to 10967 Ω.cm2 and the intact coating provided a total resistance of 80254 Ω.cm2. The dispersion-corrected Density Functional Theory (DFT)-D explorations ascertained the inclusion capacity of benzimidazole inside the β-CD. The Monte Carlo/Molecular Dynamics (MC/MD) calculations strongly affirmed the adsorption of BM and β-CD-BM over the substrate.