Behaviors of an excess proton in solute-containing water clusters were investigated using infrared spectroscopy and ab initio calculations. This investigation characterized the structures of protonated methanol-water clusters, H+(CH3OH)(H2O)(n) with n=2-6, according to their nonhydrogen-bonded and hydrogen-bonded OH stretches in the frequency range of 2700-3900 cm(-1). Ab initio calculations indicated that the excess proton in these clusters can be either localized at a site closer to methanol, forming a methyloxonium ion core (CH3OH2+), or at a site closer to water, forming a hydronium ion core (H3O+). Infrared spectroscopic measurements verified the calculations and provided compelling evidence for the coexistence of two distinct structural isomers, CH3OH2+(H2O)(3) and H3O+(CH3OH)(H2O)(2), in a supersonic expansion. The spectral signatures of them (either CH3OH2+ or H3O+ centered) are the free-OH stretching absorption band at 3706 cm(-1) of a single-acceptor-single- donor H2O, and the band at 3673 cm(-1) of a single-acceptor CH3OH. At n=4-6, the clusters adopt structures similar to their pure water analogs with five-membered rings starting to form at n=5. The position of the excess proton in them varies sensitively with the number of solvent water molecules as well as the geometry of the clusters. To further elucidate the behaviors of the excess proton in these clusters, we analyze in detail the potential energy surface along the proton transfer coordinate for two specific isomers of n=2 and 4: MW2II and MW4I. It is found that the proton can be nearly equally shared by methanol and the water dimer subunit in the form of CH3OH-H+-(H2O)(2), as substantiated by hydrogen bond cooperativity and zero-point vibrational effects.