Toxaphene is a chlorinated insecticide that is a mixture of thousands of congeners. Because of its persistence, bioaccumulation, and inherent toxicity, toxaphene is now regarded as an organic chlorinated pollutant of concern worldwide, and is one of 12 persistent organic pollutants in the Stockholm Convention. The analysis of toxaphene is still a major challenge because of the numerous congeners it contains. In the present study, analytical methods for toxaphene congeners were developed in different media. The established methods were applied to determine the levels and distribution of toxaphene residues in the various environment compartments in China. The major results are summarized below. 1. Isotope dilution gas chromatography coupled to triple quadrupole mass spectrometry was developed to accurately identify and quantify indicator toxaphene congeners (P26, P50, P62) in environmental samples. The relative standard deviations (RSD) of the target compounds were all below 15 %. A good linear relationship (r2>0.997) was observed between 10–200 µg·L-1. The range for the limit of detection (S/N=3) was 0.5–6 µg·L-1. This analytical method meets the requirements for trace analysis of toxaphene congeners. 2. Because of the complexity of toxaphene congeners, comprehensive two-dimensional gas chromatography was coupled withmicro-electron capture detector for the simultaneous analysis of 23 toxaphene congeners. The major parameters for the gas chromatograph and modulator were optimized to improve the separation of target components. Sample matrix-matched calibration was used to determine the residue contents using external standard curves. The established method showed good linearity with correlation coefficients (r2) higher than 0.99 in the concentration range of 1–200 μg/L. The limit of detection (S/N=3) ranged from 0.039 to 0.482 μg/L for individual congeners, which indicates the method has high sensitivity. The relative standard deviations of all congeners in the matrix samples were below 30 % (n = 5), and the recoveries ranged from 55 to 115 %. 3. The toxaphene contamination status in different environmental compartments in China was systematically investigated with the developed method. Eight air background sites were selected to represent mainland China according to the Guidance on the Global Monitoring Plan (GMP). Toxaphene levels were below the LOD at the background sites (detection limits P26<0.2, P50<0.5, P62<0.8 pg m-3; recovery 70–85 %). Surface soil samples (n = 769) were collected with a grid collection method from Liaoning, Jiangsu and Zhejiang provinces (China) where toxapene had been used in the past. Sediment samples (n = 71) were collected from five river basins, including the Songliao, Hai, Yellow, Yangtze and Pearl River basins. The toxaphene levels in all samples were below the LOD. To evaluate the currant toxaphene contamination status, different types of samples were collected from a former toxaphene manufacturing plant in China. Ten samples were collected, including six soil samples and four plant samples. Toxaphene congeners were analyzed by comprehensive two-dimensional gas chromatography. The total toxaphene concentration ranged from 1.1 to 103 µg g-1. Among the 23 congeners, the nonachlorobornane B9-2006 congener was the most abundant in the soil samples with a concentration range of 33–2426 ng g-1. The indicator congener concentrations were low compared with the other congeners, as follows: B8-1413 (P26), 0.54–11 ng g-1; B9-1679 (P50), 3.0–44 ng g-1; and B9-1025 (P62), 8.2–475 ng g-1. The lower chlorinated homologs were predominant in the plant samples.