An effective approach has been used to synthesize N-doped HTiNbO5 (denoted as N-HTiNbO5) with a better intercalation property. The synthesis of polyaniline (PANI) with N-HTiNbO5 to form PANI-N-HTiNbO5 lamellar nanocomposites by in situ polymerization using the aniline (ANI) intercalation compound ANI/N-HTiNbO5 as the intermediate has been investigated. The resulting PANI-N-HTiNbO5 nanocomposite showed a better crystallinity with a monolayer of PANI within the interlayers of N-HTiNbO5, because nitrogen doping can affect the surface charge distribution of [TiNbO5](-) layers. The cyclic voltammetry (CV) results indicated that the PANI-N-HTiNbO5 nanocomposite had good redox activity and electrochemical-cycling stability in acidic solution. The visible-light response of the PANI-N-HTiNbO5 nanocomposite was enhanced through N-doping, acid exchange, and the intercalation of PANI. The PANI-N-HTiNbO5 nanocomposite showed the highest activity with 97.8% methylene blue (MB) photodegraded in 170 min under visible light irradiation. The significant enhancement of photocatalytic performance can be attributed to the high efficiency of charge separation, induced by the synergistic effect between PANI and N-HTiNbO5. In addition, the PANI-N-HTiNbO5 nanocomposite had a high thermal and photodegradation stability due to the intercalation reaction at the molecular level.