By using electrospray ionization mass spectrometry (ESI-MS), it was proven experimentally that the lithium cation (Li+) forms with racemic [6] helicene (C26H16) the cationic complex species [Li(C26H16)](+). Further, applying quantum chemical DFT calculations, the most probable structure of the [Li(C26H16)](+) complex was derived. In the resulting "asymmetrical" complex, the "central" cation Li+ is bound by six bonds to six carbon atoms from the two terminal benzene rings of the parent [6] helicene ligand via cation-pi interaction. Finally, the interaction energy, E(int), of the considered cation-pi complex [Li (C26H16)](+) was found to be -248.0 kJ/mol, confirming the formation of this cationic complex species as well. (C) 2016 Elsevier B.V. All rights reserved.