Epoxy coatings are widely used for corrosion protection of metals, but under extremely harsh environments, the epoxy polymer chains such as the C-O bonds of epoxy ether and aromatic ether, and the -OH in the epoxy chain structure can also undergo aging and degradation, leading to the failure of the coating in service. How to extend the anti-aging capability of epoxy resins while maintaining their other properties unchanged has become a major challenge in the practical application of epoxy coatings. In this study, the polyaniline (PANI) modified multi-walled carbon nanotubes (MWCNT@PANI) were synthesized by polymerization in-situ and added to epoxy resin as an anti-aging filler. The various measurements have been adopted to characterize the composition and structure of MWCNT@PANI, and the anticorrosive performance of the composite coating for carbon steel were evaluated via salt spray, chemical aging and UV light aging. Results showed that the impedance value of the blank epoxy coating decreases by at least two orders of magnitude after the salt spray tests, and the contact angle decreases by about 30° and gradually changes from hydrophobic to hydrophilic, indicating a significant decline in corrosion resistance. In contrast, the composite coating confirmed the excellent anti-aging performance, while the impedance values increased by approximately 2-5 orders of magnitude compared to that in blank epoxy coatings, and remained around 1010 Ω·cm2. Given the dense encapsulation of MWCNT@PANI, the dispersion stability between the filler and EP can be improved, and the effective corrosion resistance performance was also supported by molecular dynamic simulation. Besides that, the ability of free radical quenching along with the labyrinth effect and hydrophobic interaction have also been investigated to explain the anticorrosion and anti-aging mechanism.