Resonant two-photon ionization, IR-UV hole-burning, and resonant ion-dip infrared (RIDIR) spectroscopies have been employed along with density functional theory (DFT) calculations to assign and characterize the hydrogen-bonded topologies and structures of eight benzene-(H2O)(n)(CH3OH)(m), cluster isomers (hereafter shortened to BWnMm) with n + m less than or equal to 4. The O-H stretch infrared fundamentals are used to determine the H-bonding topology of the clusters. However, in several cases, the O-H stretch spectrum leaves an ambiguity regarding the position of the methanols within the structure. In these cases, the methyl CH stretch region serves as a secondary probe capable of distinguishing among the various possibilities. For n + m = 2, a single BWM isomer is observed with OH stretch fundamentals at 3508, 3606, and 3718 cm(-1). A comparison of the methyl CH stretch transitions of BWM and BM2 reveals that the methanol in BWM accepts a H-bond from water and forms a pi H-bond with benzene. The n + m 3 results show the subtle effects that solvent composition can have on the lowest-energy structure of the cluster. Two isomers of BW2M are observed but just one of BWM2. Both water-rich BW2M isomers possess transitions characteristic of cyclic W2M subclusters in which water is pi H-bonded to benzene. Each isomer shows a set of three single-donor OH stretch transitions, a pi H-bonded OH stretch near 3650 cm(-1) and a free OH stretch (similar to 3716 cm(-1)). The two BW2M isomers differ in the position of the methanol in the H-bonded cycles. Conversely, the methanol-rich BWM2 cluster OH stretch transitions are those of a WM2 chain, with a signature n H-bonded OH stretch located at about 3590 cm(-1). The methyl CH stretch absorptions are used to deduce that the water molecule in BWM2 is in the donor position in the chain, furthest from benzene＇s pi cloud. Finally, the spectra for the n m = 4 series show systematic changes in the spectrum with changing methanol content in the cluster. In all cases, both OH stretch and CH stretch transitions point firmly to cyclic WnMm, subclusters in which one of the free OH groups on a water molecule in the cycle is used to pi H-bond to benzene.