Electrical and optical properties of In-Ga-Sn-O (IGTO) thin films deposited by radio-frequency magnetron sputtering were investigated according to annealing temperatures. While IGTO films remained an amorphous phase even after a heat treatment at temperature up to 500 °C, Hall measurements showed that annealing temperature had a significant impact on electrical properties of IGTO thin films. After investigating a wide range of annealing temperatures for samples from as-deposited state to 500 °C, IGTO film annealed at 200 °C exhibited the best electrical performance with a conductivity of 229.31 Ω−1cm−1, a Hall mobility of 36.89 cm2V−1s−1, and a carrier concentration of 3.85 × 1019 cm−3. Changes in proportions of oxygen-related defects and percentages of Sn2+ and Sn4+ ions within IGTO films according to annealing temperatures were analyzed with X-ray photoelectron spectroscopy to determine the cause of the superb performance of IGTO at a low temperature. In IGTO films annealed at 200 °C, Sn4+ ions acting as donor defects accounted for a high percentage, whereas hydroxyl groups working as electron traps showed a significantly reduced percentage compared to the as-deposited film. Optical band gaps of IGTO films obtained from UV–visible spectrum were 3.38–3.47 eV. The largest band gap value of 3.47 eV for the IGTO film annealed at 200 °C could be attributed to an increase in Fermi-level due to an increase of carrier concentration in the conduction band. These spectroscopic results well matched with electrical properties of IGTO films according to annealing temperatures. Excellent electrical properties of IGTO thin films annealed at 200 °C could be largely due to Sn donors besides oxygen vacancies, resulting in a significant increase in free carriers despite a low annealing. temperature.