Recently, the application of phosphorene structure analogues in gas sensors has been a hot research topic since the appearance of phosphorene. SnSe monolayer as one of them has been proved to be much more stable properties than phosphorene. Based on the density-functional theory, the interaction between gas molecules (CO, CO ₂ , O ₂ , NO, NH ₃ , SO ₂ and NO ₂ ) and SnSe monolayer are theoretically investigated by first-principles calculation. Macroscopically, gas molecules selective adsorption of SnSe monolayer is analyzed by molecular dynamics. Compared to CO, CO ₂ , O ₂ , SnSe monolayer performs stronger affinity for SO ₂ and NO ₂ , which possesses appropriate adsorption energies (−6.000 eV and −0.759 eV) and elevated charge transfers (−0.239 e and −0.328 e). SnSe monolayer chemical adsorption of NO ₂ , while physically adsorbing SO ₂ , is more suitable for the adsorption mode of SO ₂ sensors. Surprisingly, the adsorption amount of SO ₂ is 6 times that of NO ₂ . Therefore, the adsorption of SO ₂ is more likely to occur compared to other gas molecules. For a mixed environment of SO ₂ and NO ₂ , the adsorption quantity of SO ₂ is not significantly affected, while the adsorption of NO ₂ is inhibited. Therefore, the SnSe monolayer could be a promising candidate as SO ₂ sensors with high selectivity and sensitivity.