Antimony-doped tin oxide (Sb:SnO2) thin films with varying Sb concentrations were deposited using the spray pyrolysis technique. A comprehensive analysis of the films' elemental, structural, and optoelectronic properties is presented. All films possess a polycrystalline single-phase nature and have a tetragonal rutile structure. As Sb concentration increases, the unit cell shrinks continuously, suggesting proper substitution of Sn4+ by Sb5+. This substitution causes a continuous increase in the concentration of charge carriers and a reduction in electron mobility. X-ray photoelectron spectroscopy investigations revealed the presence of asymmetric Sn 3d core-level peaks distinguished by peak splitting, which increases with increasing carrier concentration. Utilizing the plasmon absorption model, an effective mass value of (0.51 ± 0.07)me for the conduction electron at the fermi level is obtained. With increasing Sb concentration, the optical energy gap increases gradually from 3.84 eV for undoped SnO2 to 4.35 eV for 5.0 at. % Sb. After considering the Urbach tailing phenomenon as well as the Moss–Burstein effect, this increase was attributed to the increase in Moss–Burstein energy due to increased charge carrier concentration. Our study revealed that the film doped with 2.0 at. % Sb has the best optoelectronic properties, with a figure of merit of 4.18 (Ω/cm2)−1.