Hydrogen-bonded clusters, formed above liquid methanol (Me) and ethanol (Et) mixtures of various compositions, were entrained in a supersonic jet and probed using 118 nm vacuum ultraviolet (VUV) laser single-photon ionization/time-of-flight mass spectrometry. The spectra are dominated by protonated cluster ions, formed by ionizing hydrogen-bonded Me m Et n neutrals, m = 0-4, n = 0-3, and m + n = 2-5. The structures and energetics of the neutral and ionic species were investigated using both the all-atom optimized potential for liquid state, OPLS-AA, and the density functional (DFT) calculations. The energetic factors affecting the observed cluster distributions were examined. Calculations indicate that the large change in binding energy going from trimer to tetramer can be attributed more to pair-wise interactions than to cooperativity effects.Key words: alcohol clusters, cluster formation, DFT calculations, mass spectrometry, vacuum ultraviolet laser.