AbstractMolecular Chirality is of central interest in biological studies because enantiomeric compounds, while indistinguishable by most inanimate systems, show profoundly different properties in biochemical environments. Enantioselective separation methods, based on the differential recognition of two optical isomers by a chiral selector, have been amply documented. Also, great effort has been directed towards a theoretical understanding of the fundamental mechanisms underlying the chiral recognition process. Here we report a comprehensive data examination of enantioseparation measurements for over 72,000 chiral selector‐selectand pairs from the chiral selection compendium CHIRBASE. The distribution of α = k′D/k′L values was found to follow a power law, equivalent to an exponential decay for chiral differential free energies. This observation is experimentally relevant in terms of the number of different individual or combinatorial selectors that need to be screened in order to observe α values higher than a preset minimum. A string model for enantiorecognition (SMED) formalism is proposed to account for this observation on the basis of an extended Ogston three‐point interaction model. Partially overlapping molecular interaction domains are analyzed in terms of a string complementarity model for ligand‐receptor complementarity. The results suggest that chiral selection statistics may be interpreted in terms of more general concepts related to biomolecular recognition. Chirality 16:369–378, 2004. © 2004 Wiley‐Liss, Inc.