The insertion reactions of germylene into CCl bond of 1-chorobenzene have been explored using density functional theory. Five germylene species have been chosen for systematically studying. All the stationary points were determined at the B3LYP/6−311+G (d, p) level of the theory. The results show that, the smaller the ΔE ST of germylene, the lower the barrier height, and the electropositive substituents on the germylene can increase the reaction activity and exothermicity of insertion into CCl bond of 1-chorobenzene.