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 900oC; 2) mixing of the prepared Na2Ti6O13 with titanium isopropoxide and calcining with urea at 500oC. 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.