The capillary electrophoretic (CE) separation of the inorganic anions bromide, chloride, nitrate, nitrite, fluoride, sulfate and phosphate is described in 0.005 mol/L sodium chromate electrolyte in the presence of soluble polydisperse ionic polymers (polyelectrolytes). The cationic polyelectrolytes used were as follows: poly(1,1-dimethyl-3,5-dimethylenepiperidinium) chromate, hexadimethrine chromate, poly(1,1-dimethyl-3,5-dimethylenepyrrolidinium) chromate and ((diethylamino)ethyl)-dextran chromate in the concentration range 0.004-0.6% (w/v). These polyelectrolytes were shown to be capable of reversing the direction of the electroosmotic flow as well as inducing changes in analyte electrophoretic mobility, separation selectivity, and resolution. Changes in electrophoretic mobility by as much as 25% were observed for the sulfate anion, and the resolution of fluoride and phosphate was enhanced by a factor of 7.8. In the presence of 0.05-0.17% w/v poly(1,1-dimethyl-3,5-dimethylenepyrrolidinium) chromate at pH 8, separation currents were found to increase only slightly as compared to an electrolyte containing equivalent amounts of sodium chromate. Electroosmotic flow was also found to be fairly constant (+/- 16%) in the pH range 6.55-10.02 for 0.01% (w/v) poly(1,1-dimethyl-3,5-dimethylenepiperidinium) chromate at an ionic strength of 0.04, compared to a 400% change in the absence of the polyelectrolyte. The reproducibility of the electroosmotic mobility was between 0.36 and 6% RSD, and analyte electrophoretic mobility was between 0.01 and 1.6% RSD. Peak height reproducibility was 0.2-8.0% RSD. Separation efficiencies were between 258,000 and 780,000 theoretical plates, and detection limits were between 4.4 x 10(-7) and 9.1 x 10(-6) mol/L.