Crack free, dense and transparent CdTiO3 thin films have been prepared by sol–gel technique using titanium butoxide and cadmium acetate. The formation of the CdTiO3 phase started from 500°C annealing temperature onwards. The complete orthorhombic structure of CdTiO3 was formed on Silicon (100) substrate at an annealing temperature of 600°C for 5 h. As the annealing temperature increased from 600 to 700°C, we have observed the cadmium silicate phase at the interface of Si and CdTiO3 phase. Structural, morphological and elemental evolution of these CdTiO3 thin films produced by sol–gel synthesis were characterised by grazing incidence X-ray diffraction (GIXRD), tapping mode atomic force microscopy (TMAFM), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) respectively.