The photolysis of riboflavin (RF) in the presence of acetate buffer (pH 3.8-5.6) and carbonate buffer (pH 9.2-10.8) has been studied using a multicomponent spectrophotometric method for the simultaneous assay of RF and its photoproducts. Acetate and carbonate buffers have been found to catalyze the photolysis reaction of RF. The apparent first-order rate constants for the acetate-catalyzed reaction range from 0.20 to 2.86 × 10(-4) s(-1) and for the carbonate-catalyzed reaction from 3.33 to 15.89 × 10(-4) s(-1). The second-order rate constants for the interaction of RF with the acetate and the carbonate ions range from 2.04 to 4.33 × 10(-4) M(-1) s(-1) and from 3.71 to 11.80 × 10(-4) M(-1) s(-1), respectively. The k-pH profile for the acetate-catalyzed reaction is bell shaped and for the carbonate-catalyzed reaction a steep curve. Both HCO3(-) and CO3(2-) ions are involved in the catalysis of the photolysis reaction in alkaline solution. The rate constants for the HCO3(-) and CO3(2-) ions catalyzed reactions are 0.72 and 1.38 × 10(-3) M(-1) s(-1), respectively, indicating a major role of CO3(2-) ions in the catalysis reaction. The loss of RF fluorescence in acetate buffer suggests an interaction between RF and acetate ions to promote the photolysis reaction. The optimum stability of RF solutions is observed in the pH range 5-6, which is suitable for pharmaceutical preparations.