A series of pi-hole complexes involving the NO2 group and several isolated pi systems have been evaluated at the BP86-D3/def2-TZVP level of theory. We have used ethene, ethyne and but-2-yne as electron donor moieties and nitrobenzene and 1,2,3,4,5-pentafluoro-6-nitrobenzene as electron acceptors. The SAPT and NBO analyses show that the dispersion term is the major contributor to the binding while pi(C-C)->pi*(C-N) donor-acceptor interactions also contribute to the overall stabilization. Finally several experimental examples were retrieved from the CSD highlighting the importance of this interaction. (C) 2015 Elsevier B.V. All rights reserved.