The effect that molecular chirality has on the formation of monolayer structures by pure enantiomers and their racemates at the liquid/solid interface has been investigated for two chiral compounds (1 and 2) which differ from each other by the presence or absence of an ester function in their respective molecular structures. 1 shows pseudoracemate formation when the achiral graphite support is exposed to a solution containing a racemate while 2 shows racemic conglomerate formation. This difference is rationalized in terms of the orientation of the pure enantiomers with respect to the graphite substrate and highlights the importance of molecular structure and its influence on balancing the interplay between molecular conformation and molecular packing on the surface. For 1, nonstoichiometric mixtures of both enantiomers have been investigated, and the results are discussed in the framework of the sergeant and soldiers principle. These results are important for the understanding and prediction of spontaneous resolution in monolayer systems.