The present work investigated the influence of growth time on the structural, optical, and optoelectronic properties of β-Ga2O3 films produced on Si substrates by the chemical vapour deposition method. The prepared films were characterized by X-ray diffraction, field-emission scanning electron microscope, and UV–Vis spectrophotometer. The films exhibited a mixed phase (β-α)-Ga2O3 crystal structure. The crystallite size ranged between 34.98 and 164.69 nm. The bandgap increased from 4.74 to 4.88 eV. The absorption and extinction coefficients were in the orders of 103 and 10−1, respectively. The refractive index, dispersive energy and single oscillator energy increased from 1.86 to 1.87, 19.24 to 28.64, and 8.36 to 9.54, respectively, with an increase of growth time. The oscillator strength, oscillator wavelength, third-order nonlinear optical susceptibility and dispersion of refractive index were in the orders of 10−4, 10−2, 10−10 and 10−9, respectively. The carrier concentration, optical conductivity, optical mobility, and optical resistivity were also evaluated. The real and imaginary dielectric constants, and plasmon frequency were also determined.