As the economy is making high-speed progress, and environmental issues have raised people’s attention. Long-term abuse of pesticides and plasticizers in the actual production makes them the most pervasive environmental pollution source. Moreover, this issue does severe harm to ecotope, food stuff and human and animal, etc. In this paper, to solve the residual pesticides and plasticizers issue, a fast, sensitive and effective analysis strategy that the three-dimensional fluorescence spectroscopy coupled with the chemometrics-based method was developed for simultaneous determination of thiabendazole (TBZ) and bisphenol A (BPA) in environmental water samples. This analysis strategy gives consider both high sensitivity and abundant information of three-dimensional fluorescence spectroscopy and the significant advantage of “mathematical separation” of the chemical multi-way calibration method. It can achieve the trace analysis for TBZ and BPA only need simple pretreatment. Although the fluorescence spectra of TBZ and BPA overlapped each other and unknown interferences coexisted in the matrices, reliable qualitative and quantitative results were obtained by the proposed method with the help of a significant “second-order advantage”.TBZ had a good linear relationship (r=0.999 9) in range of 20~200 ng·mL^-1, while BPA had good linear relationship (r=0.999 1) in 40~280 ng·mL^-1. In two kinds of environmental water samples, the obtained average recoveries of TBA and BPA were 96.3%~99.1% and 90.0%~90.8%, respectively. Meanwhile, the standard deviations were less than 7.2%. In order to evaluate the performances of the proposed method, the figures of merit such as sensitivity (SEN), selectivity (SEL), the limit of detection (LOD) and limit of quantification (LOQ) were investigated. The satisfactory results indicated that it might be promising as an effective strategy for rapidly and accurately quantifying TBZ and BPA in complex environmental water samples. So this work provides an effective and scientific monitoring tool for pesticides and plasticizers residues.