This paper aims to enhance the anti-corrosion of epoxy coating to steel sheet. The hollow TiO2 nanoparticles were synthesized by hydrothermal reaction and sodium fluoride sculpture. With this TiO2 was used as the substrate to load the corrosion inhibitor azimidobenzene (BTA). The TiO2 outer shell encapsulated with BTA was modified by a silicon dioxide film with ethylsilicate (TEOS) and (3-aminopropyl) triethoxysilane (APTES) as silicon sources. The microstructure, phase and structure were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (EDS), X-ray powder diffractometer (XRD), thermal gravimetric analyzer (TGA) and ultraviolet- visible spectrum (UV-Vis). The release behavior of BTA at different pH values (2, 4, 7) was investigated use ultraviolet-visible spectrum analysis. The anti-corrosion behavior of steel sheets in 0.3% NaCl solutions without and with modified TiO2 at different pH values was measured by polarization curves. The results indicated that when pH values were adjusted to 2, BTA encapsulated in nanocontainers release rate was the highest, approximately 90% of BTA released within 24 h, and the corrosion inhibition rate reached to 80.7%. Studied by using electrochemical impedance spectroscopy (EIS) showed that the epoxy@modified TiO2 coating was basically maintained within one order of magnitude during the soaking period (1~7 d) and it had better corrosion resistance than the blank epoxy coating. In conclusion, the doping of TiO2@BTA@SiO2 nanoparticles improves the corrosion resistance of epoxy resin coating and prolongs the use time of the coating.