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Based on the inhibition effect of transferrin (Tf) on the reaction of the luminol-hydrogen peroxide (H(2)O(2)) chemiluminescence (CL) system, catalysed by meso-tetra-(3-methoxyl-4-hydroxyl) phenyl manganese porphyrin (MnP) as a mimetic enzyme of peroxides, a sensitive flow-injection CL method has been developed for the determination of Tf in an alkaline medium. The CL reaction was carefully investigated by examining the variations of reaction conditions. Under optimum conditions, the linear range for the determination of transferrin was 0.04-20.0 μg/mL and the detection limit was 1.62 ng/mL. This proposed method was sensitive, convenient and simple, and has been successfully applied to the determination of transferrin in a serum sample., (Copyright © 2011 John Wiley & Sons, Ltd.)