The interaction between the chiral drug of propranolol (PPL) and alpha1-acid glycoprotein (AGP, orosomucoid) has been first studied by fluorescence spectrophotometry. The fluorescence intensity of PPL increased due to the addition of AGP into PPL. The equation of Scatchard was employed to calculate the association constant and binding site number of the two enantiomers with AGP. The association constant is 2.62 x 10(5)M-1 for R-PPL and 8.57 x 10(5)M-1 for S-PPL and the binding site number is 0.41 for R-PPL and 1.17 for S-PPL at 17 degrees C respectively. The method of thermodynamics was applied to determine the binding type of S-PPL with AGP. The results suggested that the binding type is mainly van der waals force or hydrogen bond. At last the effect of three metal cations on the association constant and the binding site number of S-PPL with AGP was examined.