The 4-aminobenzonitrile (ABN) molecule has two active sites amenable to hydrogen bonding to methanol (MeOH) and ethanol (EtOH): the amino, -NH2, and the cyano, -CN, groups. Two-color resonance enhanced multiphoton ionization time-of-flight mass spectroscopy and hole burning spectroscopy in addition to the ionization energies provides sound evidence of the occurrence of two isomers in the ABN(MeOH)(1) complex and one single isomer for the ABN(EtOH)(1) complex. Combining the outcomes from the ABN/methanol and ABN/ethanol experiments with ab initio computations at reliable theory levels one identifies the preferred solvation sites and the optimized geometries. A discussion of the role of the aliphatic chains on the geometry of the isomers and other properties is presented. (C) 2003 American Institute of Physics.