Coatings prepared from polyaniline–nano-TiO2 particles synthesized by in situ polymerization were found to exhibit excellent corrosion resistance much superior to polyaniline (PANI) in aggressive environments. The corrosion studies were carried out on steel plates coated with these formulations containing 10 wt% polyaniline prepared with different concentrations of nano-TiO2. The electrochemical impedance spectroscopy was studied at periodic intervals during exposure to hot saline (65 °C) conditions for prolonged durations over a period of 90 h. The open circuit potential (OCP) was found to shift with time from −0.38 V SCE to more anodic side (−0.2 V SCE) much above that of bare steel (−0.5 V SCE). The presence of nano-TiO2 was found to be vital in the prevention of corrosion and the shift of OCP to anodic side. From these data, one could envisage more than 100 times improvement in the corrosion resistance especially for polyaniline prepared with 4.18 wt% nano-TiO2. The exceptional improvement of performance of these coatings has been associated with the increase in barrier to diffusion, prevention of charge transport by the nano-size TiO2, redox properties of polyaniline as well as very large surface area available for the liberation of dopant due to nano-size additive.