Highly transparent TiO2/SiO2 films prepared using sol-gel technique doped with organic azo dye, Disperse Red 1(DR1) have been investigated. Processing parameters such as spin speed, spin time, and ambient atmosphere, and solution synthesis parameters such as catalysis method, alcohol dilution ratio, and component molar percentages, may affect the film formation. The refractive index increases follow along with the raising of the molar ratio between TiO2 and SiO2. When the molar ratio between TiO2 and SiO2 is zero, i.e. no titania precursor in the initial solution, the refractive index is minimum 1.49 at 1300nm, whereas when there is no TEOS in the initial solution, the refractive index is maximum 1.81 at 1300nm. The sol-gel thin film is spin-coated on ITO glass substrate with better uniformity. The electric-optic coefficient γ33=42pm/V was measured by simple reflection technique at a fundamental wavelength of 1300nm. The hybrid organic-inorganic sol-gel film is well balanced material in its simplicity for film formation, nonlinearity, and thermal stability sufficient for device fabrication. Moreover, the measurement system was calibrated and the measured electric-optic coefficient of the gallium arsenide crystal is in excellent agreement with the known value.