Binding energies and configurations of ckiral hydrocarbons adsorbed on stepped Pt surfaces are calculated using Monte Carlo simulations. McFadden et al. have recently shown that many stepped single-crystal surfaces have chiral characteristics and that chiral molecules adsorbed, on these surfaces should display enantiospecific properties [McFadden, C. F.; Cremer, P. S.; Gellman, A. J. Langmuir 1996, 12, 2483]. The results presented here protide the first theoretical predictions of this phenomenon by measuring enantiomeric shifts in the binding energies of chiral hydrocarbons on chiral Pt surfaces. Multiple examples of enantiomeric shifts that should be readily detectable using temperature-programmed desorption experiments are identified. The role of adsorbate size and surface structure on the magnitude of enantiomeric shifts in binding energies is discussed.