Noncovalent interactions have attracted widespread interest due to its essential role in crystal engineering,supramolecular synthesis,and structure-based drug design [1].Recently,σ-hole [2] and π-hole [3] interactions as new types of interactions,have attracted more and more attention.The second order M(o)ller-Plesset perturbation theory(MP2)calculations and “quantum theory of atoms in molecules”(QTAIM)studies have been performed to discuss the cooperativity between the σ-hole and π-hole interactons in the ClO…XONO2/XONO…NH3(X= Cl,Br,I)complexes.The electrostatic interaction plays an important role in the σ-hole and π-hole interactions.The interaction energies,binding distances,infrared vibrational frequencies,electron densities ρb and its Laplacians ▽2ρb at the bond critical points of the σ-hole and π-hole interactions demonstrate that the negative cooperativity exist between these interactions.