The characteristics of CoTiO3 high- k dielectric prepared by sol-gel spin coating method had been demonstrated. High electrical permittivity (k∼40.2) of CoTiO3 dielectric was extracted via the transmission electron microscopy image and capacitance-voltage curves. In addition, the valence band offset between thermal SiO2 and spin-on CoTiO3 was about 4.0 eV, which was detected by x-ray photoelectron spectroscopy. The band gaps of thermal SiO2 and spin-on CoTiO3 were 9.0 and 2.2 eV, respectively. Energy band alignment of spin-on CoTiO3 directly with SiO2 and indirectly with Si was determined in this work.