Electrically conductive HCl-doped polyaniline (Pani)@titanium dioxide (TiO2) nanocomposites were prepared by the in-situ oxidative polymerization of aniline in the presence of different amounts of TiO2 nanoparticles. The synthesized Pani@TiO2 nanocomposites were confirmed by transmission electron microscopy, X-ray diffraction, UV-visible spectroscopy, and thermogravimetric analysis. The stability of the Pani@TiO2 nanocomposites in terms of their electrical conductivity retention was examined under isothermal and cyclic aging conditions, and compared with that of pure Pani. The Pani@TiO2 nanocomposites showed higher thermal stability than pure Pani. The effect of competitive doping/de-doping by TiO2 was examined at different Pani to TiO2 weight ratios. TiO2 at a higher weight percentage was found to be involved in the de-doping type of interaction with Pani, leading to its neutralization, which was found to be similar to the de-doping phenomenon, as in the case of neutralization in basic media. The novel mechanism for this de-doping type of interaction of TiO2 with Pani was also proposed.