Transition metals in highest oxidation state complexes have been considerably used in the analysis of several organic compounds and initiator of graft copolymerization.In this work,it is found that some transition metals in highest oxidation state complexes,for example,dihydroxydiperiodatocuprate(DPC）,dihydroxydiperiodatonickelate(DPN） and dihydroxydiperiodatoargentate(DPA）,are good oxidants which can react with luminol to emit chemiluminescence(CL） in alkaline mediums.The CL intensity could be greatly sensitized by some aminoglycoside antibiotics.The application of the CL system was studied by using luminol-DPC-tobramycin as a model，and a new CL method for the determination of tobramycin in human serum was proposed by combining with the flow injection technology.Effect of reagents concentration on CL intensity was investigated.Under the optimum experimental conditions,the CL intensity was proportional to tobramycin concentration over the range of 6.0×10-8 – 2.0×10-6 g/mL with a detection limit(3σ） of 1.5×10-8 g/mL.The proposed method had a good reproducibility for 5.0×10-7 g/mL tobramycin with relative standard deviation(RSD,n=7） of 2.7%.It was successfully applied in the determination of tobramycin in human serum.