The competitive adsorption of long-chain (C-18 and C-24) carboxylic acids versus n-decanol on graphite was investigated using frequency-modulation atomic force microscopy. A long-range-ordered monolayer of the solute (stearic acid or lignoceric acid) developed in saturated decanol solution, whereas an ordered decanol monolayer was deposited from dilute solutions. The piconewton-order tip-surface force was observed in solutions as a function of the vertical and lateral coordinates, together with the topography of the monolayers. The tip-surface force was periodically modulated, which was interpreted with a solution structure commensurate with the ordered assembly of adsorbed monolayers. These results show that the solution structure at the interface was controlled by the competitively adsorbed species and thus was sensitive to the composition of the bulk solution.