van der Waals complexation in a supersonic expansion combined with laser-induced fluorescence techniques have been used to discriminate between isolated diastereoisomer pairs of weakly bound species. By using 2-naphthyl-1-ethanol (2-NetOH) as the chiral chromophore, we have investigated the effect of complexation with different aliphatic alcohols on the microscopic shifts of the S-0-S-1 transition and on the fluorescence decay times of the chromophore. The fluorescence excitation spectra of the complexes of 2-NetOH with nonchiral primary alcohols have been first examined, and the binding energy of the complex of Z-NetOH with methanol has been determined to be on the order of 1000 cm(-1). In the case of complexation with chiral solvents such as 2-methyl-1-butanol or secondary alcohols, the homochiral and heterochiral pairs give rise to specific spectral shifts and patterns which allow them to be clearly distinguished. The fluorescence lifetimes following; excitation of alcoholic complexes in every case are longer than those of the uncomplexed chromophore and also depend on the particular diastereoisomer excited. The chiral recognition evidenced on the spectral properties and on the dynamical relaxation processes of isolated enantiomeric pairs shows the nonequivalence of their interaction energy in both the ground and excited states. The nature of the stereochemically dependent interactions can be tentatively described on the grounds of a hydrogen bonded intermolecular structure involving a folded geometry of the alkyl chain with respect to the naphthalene nucleus.