In this study, the enantioselective retention behaviors of methyl mandelate (MM) and benzoin (B) were investigated using Chiralpak IB as a sorbent and ethanol, 1-propanol, and 1-butanol as solvent modifiers in the normal-phase mode. For both MM and B, similar chiral recognition mechanisms were observed, potentially involving at least two types of chiral adsorption sites. With a retention model describing local retention behaviors, an enantioselectivity model based on a three-site model was proposed to describe the data. Fitted parameters were also used to analyze the contributions of each type of adsorption site to the apparent retention behavior. Combining the local retention model with the three-site model provided a qualitative and quantitative explanation for the correlation between modifier concentration and enantioselectivity. Overall, our results indicated that heterogeneous adsorption mechanisms are a key aspect in understanding enantioselective retention behaviors. Distinct local adsorption sites contribute differently to apparent retention behaviors, with these contributions being influenced by the mobile phase composition to varying degrees. Hence, enantioselectivity changes with variations in modifier concentration.