An understanding of collective influence of Fe-loading and calcination on changes in the crystal structure, morphology, phase composition, and photocatalytic activity of titanate-nanostructures is investigated here. Bare sodium-titanate nanotubes (TNT) having a BET-surface-area (SBET) of 176 m2 g−1 were transformed to sodium-titanate nanorods (TNT(S)) of SBET = 21 m2 g−1 when calcined at 800°C. Whereas, calcination of Fe-loaded-TNT at 800°C led to a variety of fragmented particles having different crystal structures, SBET (21–39 m2 g−1), shape, and sizes (50–70 nm) attributed to the strain induced thermal-decomposition of TNT after Fe-loading. The comparative photocatalytic activity of as-prepared catalysts under UV-light irradiation was evaluated by photooxidation of naphthalene to CO2, with the identification of its photoproduced intermediates by GC-MS analysis. These results are well explained in correlation with the surface area, size, and shape of as-prepared catalysts.