N-doped Na₂Ti₆O₁₃@TiO₂ (denoted as N-NTO@TiO₂) composites are successfully synthesized using a simple two-step process: 1) ball-milling of TiO₂ with Na₂CO₃ followed by heat treatment at 900°C; 2) mixing of the prepared Na₂Ti₆O₁₃ with titanium isopropoxide and calcining with urea at 500°C. The prepared composites are characterized using XRD, SEM, TEM, FTIR, and BET. The N-NTO@TiO₂ composites exhibit well-defined crystalline and anatase TiO₂ with exposed {101} facets on the external surface. Moreover, dopant N atoms are uniformly distributed over a relatively large area in the lattice of the composites. Under visible light irradiation, ~51% of the aqueous methylene blue is photodegraded by N-NTO@TiO₂ composites, which is higher than the values shown by other samples because of the coupling effects of the hybridization of NTO and TiO₂, N-doping, and presence of anatase TiO₂ with exposed {101} facets.