Chlorpromazine reacts with Eriochrome Cyanine R forming an ion association compound, insoluble in water but fairly soluble in buthyl alcohol. In this work the optimal reaction and extraction conditions were established. The spectroscopic studies of the formed compound were performed by UV, VIS, IR,1H NMR and13C NMR spectrometry. The new extractive-spectrophotometric method for chlorpromazine hydrochloride determination is proposed. Using this method it is possible to determine chlorpromazine hydrochloride concentration in the range 7.0–70 μg/ml. This method was verified against the method of Blazek and applied to determination of chlorpromazine hydrochloride in pharmaceuticals.