A flow-injection analysis chemiluminescence method based on the enhancement effect of the flumequine-Tb(III) complex on the weak native emission of the Ce(IV)-Na2SO3 system has been developed for the determination of flumequine. The method includes a cleanup and preconcentration stage (750-fold) of the sample by hollow-fiber liquid-phase microextraction using an Accurel(®) Q 3/2 polypropylene hollow fiber impregnated with 1-octanol as the supported liquid membrane. The obtained 50 μL acceptor phase was injected in a 1 mM Tb(III) + 4 mM Ce(IV) in 5% v/v H2 SO4 stream and mixed with a 2 mM Na2 SO3 stream before its introduction into the flow cell. The chemiluminescence signal was linear in the 0.3-15 ng/mL range, with detection and quantitation limits of 0.1 and 0.3 ng/mL, respectively. The method allows the selective extraction and determination of flumequine in wastewater samples, using simpler and lower-cost instrumentation and with shorter extraction and analysis times than traditional high-performance liquid chromatography analysis.