Ab initio calculations have been performed to study the complexes of XeOF2 and a series of pi systems including ethyne, ethene, benzene, pyrrole, furan, and thiophene. More than two structures were obtained for each complex with an aerogen-pi bond. The configuration of complex has a significant effect on its stability. The strength of aerogen-pi interaction is comparable with that of lone pair-aerogen interaction and conventional hydrogen bonds. A breakdown of the aerogen-pi interaction attributes its stability to approximately equal parts electrostatic and polarization energies, with a relatively smaller contribution from dispersion energy. (C) 2016 Elsevier B.V. All rights reserved.