Ion-association complexes of Naphazoline HCl (I), Tolazoline HCl (II) and Xylometazoline HCl (III) with [Co(NO2)(6)](3-) and [Fe(CN)(6)](3-) were precipitated and the excess of the unreacted iron or cobalt comples was determined. A new method using atomic emission and atomic absorption spectrometry for the determination of the above drugs in pure solutions and in pharmaceutical preparations is given. The drugs have been determined in the ranges 0.98-14.76, 0.78-11.80 and 1.12-16.80 mu g/ml solutions of I, II and III, respectively, using [Co(NO2)(6)](3-)], With mean relative standard deviations of 0.4-1.5% and 1.92%-19.68, 1.52-5.68 and 2.24-22.4 mu g/ml solutions of I, II and III, respectively using [Fe(CN)(6)](3-); with mean relative standard deviations of 0.6-1.6%. The recovery values of 98.12-101.26% indicate high precision and accuracy.