For the first time, crack free, dense and transparent polycrystalline rhombohedral NiTiO3 single phase structure thin films have been prepared by a sol-gel method using titanium isopropoxide and nickel acetate. The formation of the NiTiO3 phase started from 750 degreesC onwards along with unreacted TiO2 in the films. The complete rhombohedral structure of NiTiO3 was formed on a silicon(100) substrate at an annealing temperature of 1000 degreesC for 5 h. As the annealing temperature increased from 900 degreesC to 1000 degreesC, we did not observe any kind of silicate phases due to silicon diffusion at the interface of the Si and NiTiO3 phase. Structural, morphological and elemental evolution of these NiTiO3 thin films produced by the sol-gel synthesis were characterized by grazing incidence X-ray diffraction, tapping mode atomic force microscopy and X-ray photoelectron spectroscopy, respectively.