Hydrothermal growth of hexagonal ZnO nanorods on the annealed titanate nanotube films is reported as a function of molar ratio of Zn(NO3)2 and methenamine (1:1–1:4). The molar ratio of 1:4 results in a dense and thinner rod in comparison with other molar ratios. Corn-like structures of the rods are believed to be due to the higher amine concentration. Raman peaks at 437 and 331 cm1 are assigned to E2 and E2H–E2L modes. Near band gap edge and green photoluminescence emission indicates the structural and oxygen vacancy. O 1s peak is found built-up of sub-peaks at 530.62, 531.8 and 532.84 eV corresponding to O2 on normal wurtzite structure and OH and oxygen vacancies of ZnO, respectively.