Studies on low-cost sol–gel spin-coated TiO₂ thin film with high refractive index (HRI), which may be used as an intermediate layer to enhance the light extraction efficiency (LEE) of a typical bottom-emitting organic light emitting diode (OLED), are reported. The TiO₂ solution is prepared using titanium tetra iso-propoxide, acetic acid, and ethanol. Spin coating method is used to deposit TiO₂ thin films on glass substrate. Different optical characterizations of as-deposited and annealed (150°C, 300°C, and 450°C) TiO₂ thin films on glass substrate are done, from which different properties of the film are derived. Ellipsometric measurement shows shrinkage in the thickness of the as-deposited TiO₂ films after annealing at different temperatures. X-ray diffraction reveals amorphous TiO₂ formation for all the samples. The RI of the coated film increases with the increase in annealing temperatures. Its value at 633 nm wavelength for the as-deposited film is found to be 2.1, which is quite high and it is seen that this RI can be further increased to 2.78 by annealing the samples at 450°C. This value is comparatively high compared to several other reported values of other researchers. The as-deposited sample reveals highest porosity, which further decreases with rise in annealing temperature. Our calculation of LEE for a typical OLED with the intermediate layer of this HRI as-deposited TiO₂ film shows improvement of the LEE. However for annealed films, the experimentally obtained thicknesses are not adequate for this improvement, but it is shown that by increasing the film thickness, further improvement of LEE is possible.