Gallium(III) oxide is a promising functional wide-gap semiconductor for high temperature gas sensors of the resistive type. Doping of Ga2O3 with tin improves material conductivity and leads to the complicated influence on phase content, microstructure, adsorption sites, donor centers and, as a result, gas sensor properties. In this work, Ga2O3 and Ga2O3(Sn) samples with tin content of 0–13 at.% prepared by aqueous co-precipitation method were investigated by X-ray diffraction, nitrogen adsorption isotherms, X-ray photoelectron spectroscopy, infrared spectroscopy and probe molecule techniques. The introduction of tin leads to a decrease in the average crystallite size, increase in the temperature of β-Ga2O3 formation. The sensor responses of all Ga2O3(Sn) samples to CO and NH3 have non-monotonous character depending on Sn content due to the following factors: the formation of donor centers and the change of free electron concentration, increase in reactive chemisorbed oxygen ions concentration, formation of metastable Ga2O3 phases and segregation of SnO2 on the surface of Ga2O3(Sn) grains.