In this study, the aging process of a surface-functional titanium dioxide nanosheet (f-TNS) composited room-temperature-vulcanized silicone rubber (RTV) composite coating was simulated in a NO2 generation device, and then the electrochemical impedance spectroscopy (EIS) of the aged composite coating was tested in a 3.5% NaCl solution. The water permeation process was analyzed by the changes in the impedance modulus, porosity, and breakpoint frequency of the composite coating. The experimental results show that the water permeability of aged RTV decreases first and then increases with the increase in the composite proportion of f-TNS. When the composite proportion of TNS was 0.3 wt.%, the composite sample had the minimum water permeability and the best resistance to NO2 corrosion. The effect of TNS on the NO2 aging resistance of RTV composites and its mechanism were studied by SEM, FT-IR, and XPS. The impedance modulus and porosity of the aged 0.3% f-TNS/RTV, respectively, were 1.82 × 107 Ω cm2 and 0.91 × 10−4%, which increased by 2.23 times and decreased by 0.37 times, respectively, compared with the values of aged pure RTV sample. In addition, the breakpoint frequency of the aged 0.3% f-TNS/RTV also significantly reduced to 11.3 Hz, whereas it was 35 Hz in aged pure RTV.