The stability of micellar solutions of amiodarone hydrochloride in the presence of polysorbate-80 and benzyl alcohol was studied using fluorescence spectrometry with λex = 420 m and λem = 506 nm. A formation scheme for mixed micelles consisting of nonionizable surfactant polysorbate-80 and cationic amiodarone with chloride counterion was proposed. Benzyl alcohol was found to lower the stability of the mixed micelles and lead to crystallization of amiodarone hydrochloride. The counterion was replaced in the presence of acetate so that crystals of amiodarone acetate with a characteristic band for acetate carbonyl stretching vibrations νC=O at 1734 cm–1 were formed. The solubilities of amiodarone hydrochloride and acetate in H2O at 20°C were determined to be 0.33 and 0.058 mg/mL. A change of the amiodarone hydrochloride to polysorbate-80 mole ratio and avoidance of benzyl alcohol and acetate-containing solutions are recommended to improve the stability of the parenteral dosage form.