Polyaniline (PANI)/HTiNbO5 lamellar hybrid nanocomposite was synthesized by the intercalation of aniline monomer into the layer structure of HTiNbO5 followed by the subsequent in situ polymerization of aniline in the interlayer spacings. The synthesis process, the structure and morphology characterizations for lamellar hybrid nanocomposite were investigated by means of XRD, FTIR, TG-DTA, and SEM. Based on the experimental results, a detailed description of the conformation of polyaniline chains within the confined galleries of the inorganic host material was presented. TG analysis showed improved thermal stability for the intercalated nanocomposite in comparison with the pure PANI. Electrochemical studies indicated that the nanocomposite exhibited good redox activity and electrochemical-cycling stability.