The gas phase geometries of ethylene glycol-water (EGmW n) (where m = 0-4, n = 0-4; m + n ≤ 4) clusters adsorbed on a fragment of carbon nanotube have been investigated using density functional theory based M05-2X and ωB97XD methods employing various basis sets. With a view to assess the effect of curvature on the hydrogen bonding pattern between ethylene glycol and water molecules, calculations on intermolecular complexes comprising a planar aromatic surface and EGmWn clusters have been carried out. Results obtained from the electronic structure calculations and Bader’s electron density analysis reveal that C-H⋯π, O-H⋯π and lone pair⋯π interactions are predominant in the stabilization of EGmWn and the corresponding complexes with fragments of a carbon nanotube and graphene. Further, the role of the π-cloud on the stability of EGmWn is illustrated by comparing the interaction energies of clusters in the presence and absence of an aromatic surface. © 2013 The Royal Society of Chemistry.