Abstract: Density functional theory (DFT) calculations were performed to study the mechanism and potential energy surface of the addition reactions between stannenes and some nucleophilic reagents (H₂O, MeOH and PhOH), and the influence of substituents at Sn or C atoms of Sn=C double bond on the potential energy surface was investigated. The results demonstrated that the monomer, dimer or trimer of H₂O or MeOH may behave as nucleophilic reagent toward stannenes, while only the monomer of PhOH can react with stannenes. The electron-withdrawing or electron-donating groups at Sn atom of Sn=C double bond can lower or elevate the Gibbs free energies of activation, respectively.However, the effects of substituents at C atom are just the reverse. The addition reactivity of three nucleophilic reagents involves in this research arranges as follows: MeOH > H₂O > PhOH.