Electrospray ionization (ESI) has been employed to produce Li+(CH3OH)(m) for infrared spectroscopic studies using a vibrational predissociation spectrometer. A gradual blue shift of the CO stretching frequency from 1023 cm(-1) to 1027 cm(-1) was observed as m increases from 5 to 10, supporting the suggestion the formation of the second solvation-shell in Li+(CH3OH)(5), in accord with the prediction by density functional theory calculations performed at the B3LYP/6-311+G**//6-31+G* level. We demonstrate in this work that the ESI source is applicable not only to the infrared study of Li+(CH3OH)(m) but also to other alkali metal methanol cluster ions as well. (C) 2004 Elsevier B.V. All rights reserved.