Hollow fiber-based liquid-phase microextraction (HF-LPME) is a relatively new technique employed in analytical chemistry for sample pretreatment which offers more selectivity and sensitivity than any traditional extraction technique. This paper describes a three-phase HF-LPME method for ibuprofen using a polypropylene membrane supporting dihexyl ether followed by a chemiluminescence (CL) determination using the CL enhancement on the acidic permanganate-sulfite system in a FIA configuration which is the first time that both techniques have been combined for analytical purposes. The CL intensity (peak area) was proportional to the log of ibuprofen concentration in the donor phase over the range 0.1-20 microg mL(-1). The detection limit was 0.03 microg mL(-1) of ibuprofen in the donor phase. The method was satisfactory reproducible and has been applied to the ibuprofen determination in pharmaceuticals and in real human urine samples.