In the present study, a DLLME method combined with the spectrophotometry was established for the preconcentration and rapid determination of total iron using 5-Br-PADAP as the complexing reagent. Compared with the cloud point extraction (CPE), additional heating or other treating procedure can be avoided. The present method for the determination of iron has a good sensitivity and selectivity with a wider linear range and has a good reproducibility and repeatability.