The application of the exterior frontier orbital extension model (EFOE model) to π-facial stereoselection of cyclohexanones with a polar substituent at C3 or C4 have been described. The theoretical prediction that a linear correlation should exist between the π-facial ( axial and equatorial) difference in the square of the EFOE densities ( λ = EFOE( ax) 2 − EFOE( eq) 2) and experimentally obtained facial selectivity (ln( ax/eq)) has been demonstrated for 5-substituted 2-decalones ( 1), 4-substituted cyclohexanones ( 2) and 3-substituted cyclohexanones ( 3). In addition, facial stereoselection of 3, where the substituent is located closer to the reaction center compared with those of 1 or 2, showed remarkable dependence on steric effects evaluated by the π-plane-divided accessible space (PDAS), another important quantity of the EFOE model, which represents simple summation of the π-plane-divided exterior three-dimensional space nearest to the reaction center outside the van der Waals surface of the substrate.