For the determination of iodide in urine, where 80-90% of consumed iodine is excreted, a fast, simple, and sensitive method of capillary zone electrophoresis was elaborated and tested also for additional complex matrices such as human serum, cooking salt, and seawater. Several approaches were examined for the separation of iodide from other macro- and microcomponents in the tested matrices, and the best results were obtained when host-guest interaction with alpha-cyclodextrin or ion-pairing with polyethylenimine was employed. In both cases comparable resolution and sensitivity were reached. Due to the relatively high price of cyclodextrin only the method with polyethylenimine was further optimized and a simple procedure enabling the determination of iodide in untreated human urine, serum, cooking salt, and seawater was elaborated. The samples were injected for 20 s at 0.5 psi (3.45 kPa) into a fused-silica capillary (0.18 mm ID, 50 cm effective length) coated with polyacrylamide (electroosmotic flow < 2 x 10(-9) m(2)V(-1)s(-1)) and filled with the optimized background electrolyte composed of 20 mM KH(2)PO(4) and 0.7% m/v polyethylenimine. For detection, UV absorption at 200 and 230 nm was measured. Concentration limits of detection reached at 230 nm were for human urine 0.14 microM, for human serum 0.17 microM, for seawater 0.17 microM, and for cooking salt 89 nM. Relative standard deviations of iodide peak area and height in all matrices ranged within 0.93 to 4.19%.