Enantiomeric separations of the adrenergic compounds adrenaline, noradrenaline, and isoprenaline were studied. Electromigrative separations were performed in uncoated fused silica capillaries using streptomycin-modified gold nanoparticles (ST-AuNPs) as an additive to the background electrolyte. The ST-AuNPs are shown to serve as an effective chiral selector. The modified AuNPs were characterized in terms of size and zeta potential, and by IR and UV-vis spectra. The effects of ST-AuNP concentration, pH value, temperature, and separation voltage on the separations were systematically studied. Under optimized experimental conditions, racemic mixtures of the respective adrenergic drugs were baseline-separated within 7 min with a resolution of up to 7.5. The relative standard deviations of the resolution in inter-day and intra-day studies (n = 5) were generally <5%. Graphical abstract Schematic of the method for enantiomeric separations. (A): At low concentrations of streptavidinylated gold nanoparticles (ST-AuNPs), the better matching enantiomer is preferably "transported" by the ST-AuNPs; (B) ST-AuNP concentration increased to an optimal value; (C): The ST-AuNP concentration is too high; even poorly matching enantiomers will be transported simultaneously.