In this paper, four composite coatings of nano-SnS/polyvinylbutyral (PVB), nano-MoS₂/PVB, nano-SnS-Zn/PVB, and nano-MoS₂-Zn/PVB were prepared, and their anti-corrosion mechanism was analyzed by experimental and theoretical calculations. The results of the electrochemical experiments show that the effect of nano-MoS₂ on the corrosion protection performance of PVB coating is better than that of nano-SnS in 3% NaCl solution, and that the addition of Zn further enhances this effect, which is consistent with the results of weight loss measurements. Furthermore, the observation of the corrosion matrix by the field emission scanning electron microscope (FESEM) further confirmed the above conclusion. At last, the molecular dynamics (MD) simulation were carried out to investigate the anti-corrosion mechanism of the nanofillers/PVB composites for the copper surface. The results show that both nano-SnS and nano-MoS₂ are adsorbed strongly on the copper surface, and the binding energy of nano-MoS₂ is larger than that of nano-SnS.