The mixing behavior of binary combinations of linear alcohols adsorbed from their liquids is studied by calorimetry and scanning tunneling microscopy (STM). In particular, we consider combinations of primary alcohols that differ by a single methylene group. Where the shorter alcohol has an odd number of carbon atoms, the combination is found to mix, essentially, ideally on the surface. However, for combinations where the shorter alcohol has an even number of carbon atoms, we find that there is molecular complex formation for shorter members but ideal mixing for longer (n > 12) homologues. This extends previous work in this area by the determination of the limits of surface molecular complex formation. We also exploit STM to address this unexpected complex formation.