A layered titanate, K2Ti4O9, is intercalated with various n-alkylamines through ion-exchange reaction in aqueous medium. On heating, the intercalated amine is partially deintercalated, yielding nitrogen-doped amine-intercalated titanates. The modified titanates are studied as catalysts in methylene blue degradation under UV irradiation. Heat-treated long-chain amine titanates exhibit better photocatalytic activity in comparison to short chain amine titanates. The improved catalytic activity could be attributed to two factors: (i) increased surface access as the titanate layers are well separated, pillared by the alkylamine chains and (ii) nitrogen doping.