Methyl and ester substituents which sit on the porphyrin ring define one groove on each face near the ruthenium center of the chiroporphyrin. Ethanol binds within one of the clefts by multipoint interaction involving O-H ... O and C-H ... O hydrogen bonds in addition to Ru-O coordination. Enantioselective binding of chiral aliphatic alcohols is observed, and the recognition of the (R)-enantiomer of 2-octanol is explained by van der Waals contacts of its n-hexyl substituent which fits nicely in the groove.