It was reported that synthesis and characteristics of two new chromogenic reagents: 4-nitryl-4′-azobenzene–diazoaminoazobenzen (NADAB )、4-nitryl-4′-azobenzene– diazoaminomethylazobenzen (NADMAB). This two reagents were all the derivatives of diazoaminoazobenzen, and we primary study the synthesis methods in the non-aqueous media and carry through structural identification of the three reagents. Grow the reagent structure conjugate surface by increasing the benzene ring, inject the substituting group into the molecular structure, thus the sensitivity as well as the selectivity are enhanced. Comparing the heterocyclic ring azo class triazene, four benzene ring class triazenes have the high sensitivity, the molar absorption absorptivity may achieve 2.0×105 L·mol – 1·cm- 1.In this paper, the spectrophotometric application of NADAB and NADMAB was investigated in detail. In the presence of the non-ionic surfacetant OP and in the Na2B4O7-NaOH medium of pH=10.0.NADAB formed a stable green complex with Ni(Ⅱ) with the molar ratio of 1:2. The maximum absorption wavelength of the complex is at 588 nm and the apparent molar absorption coefficients of the complex is 2.0×105 L·mol-1·cm-1.Beers law is well obeyed in the range of 0.6～7.5μg/L for nickel. In the presence of the non-ionic surfacetant OP and in the Na2B4O7-NaOH medium of pH=10.5 NADAB formed a stable violet complex with Cd(Ⅱ) with the molar ratio of 1:2. The maximum absorption wavelength of the complex is at 578 nm and the apparent molar absorption coefficients of the complex is 2.0×105 L·mol-1·cm-1.Beers law is well obeyed in the range of 0.2～12.5μg /L for cadmium. In the presence of the non-ionic surfacetant OP and in the Na2B4O7-NaOH medium of pH=10.0 NADAB formed a stable complex with Cu(Ⅱ) with the molar ratio of 1:2. The maximum absorption wavelength of the complex is at 570 nm and the apparent molar absorption coefficients of the complex is 1.240×105 L·mol-1·cm-1.Beers law is well obeyed in the range of 0.3～8.0μg /L for copper. In the presence of the non-ionic surfacetant Tritonx-100 and in the Na2B4O7-NaOH medium of pH=10.0 NADMAB formed a stable violet complex with Cd(Ⅱ) with the molar ratio of 1:1. The maximum absorption wavelength of the complex is at 576 nm and the apparent molar absorption coefficients of the complex is 2.5×105 L·mol-1·cm-1.Beers law is well obeyed in the range of 2.5～20μg /L for cadmium. In the presence of the non-ionic surfacetant Tritonx-100 and in the Na2B4O7-NaOH medium of pH=10.5 NADMAB formed a stable complex with Cu(Ⅱ) with the molar ratio of 1:2. The maximum absorption wavelength of the complex is at 585 nm and the apparent molar absorption coefficients of the complex is 0.724×105 L·mol-1·cm-1.Beers law is well obeyed in the range of 1.5~10.0μg /L for copper.In this article, NADAB was used as high sensitive reagent for simultaneous determination of trace volumes of Ni(Ⅱ)、Cd(Ⅱ) and Cu(Ⅱ). Because the absorption spectrum overlapped seriously. The absorbancy and the density of the mixed-ion were not appear linearity. So we use Radial basis function network and Ni(Ⅱ)、Cd(Ⅱ) and Cu(Ⅱ) could be directly determined simultaneously in the water solution by the new method. This method have high sensitivity and high accuracy, the results were satisfied.