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Tin dioxide (SnO2) and rare earth (Y, La, Pr, Tb, and Er)-doped SnO2 materials were synthesized by a solvothermal method and used for gas sensors. The effect of rare-earth (RE) doping on structural, electronic, and gas-sensing properties of SnO2 has been investigated. According to a comparative study on the gassensing properties of SnO2 and RE-doped SnO2 gas sensors to various testing gases, the RE-doped SnO2 sensors showed enhanced sensitivities to different testing gases. Especially, the Pr-doped SnO2 sensor exhibited outstanding sensing properties to SO2, including a high response of 19.5-50 ppm SO2, excellent selectivity, repaid response and recovery rates, and superior long-term stability. According to the structural analyses, DFT calculation, and the electrochemical measurement of the SnO2 and Pr-SnO2 materials, the improved electron excitation efficiency endowed the Pr-SnO2 with a high density of free electrons that can be trapped by atmospheric oxygen species and participated in SO2-sensing reactions. Moreover, after the Pr doping of SnO2, the enhanced charge carrier transport properties, including prolonged electron lifetime, improved electron diffusion coefficient, and increased effective diffusion length, were conducive to improving the SO2-sensing property.