The purpose of the program is: (1) to establish and improve groundwater and other environmental water, sampling and analysis of persistent organic pollutants, and related background data to provide environmental agencies in the future when amending or standards developed in the sampling method reference; (2) to compare the results of two-fold analysis of the sampling method NIEA W790.50B and compare the differences between centrifugal and non-centrifugal sampling methods; (3) to evaluate the timing of the use of the centrifuge and to incorporate it into the draft revision of the sampling method. The program has completed investigations on such high pollution potential areas as 7 plants producing effluent and 1 monitoring well. The analysis showed that PCDD/Fs concentration in the effluent was 0.017 ~ 21.3 pg WHO-TEQ/L, and the WI-03 medical waste incinerator was the highest; the concentration of DL-PCBs was ND ~ 0.308 pg WHO-TEQ/L; the PBDEs concentration was 298 ~ 9315 pg/L, both of which were the highest for WI-04. The program has also investigated the concentration of persistent organic pollutants (POPs) in groundwater of the decabromodiphenyl ether plant (BDE-02) and found that the concentration of pollutants was high, among which the dioxin content was 0.090 and 0.115 pg WHO-TEQ/L while the content of polybrominated diphenyl ethers was as high as 10.2 and 167 ng/L, indicating the presence of residual brominated flame retardants in the area. As for the results of two-fold analysis of the sampling method, there were no significant differences in the concentrations of PCDD/Fs and DL-PCBs measured after simultaneous sampling of the two devices, and another set of centrifugal samples was also taken at the time of sampling to evaluate the effects of the inclusion of the centrifuge on the sample concentration. The results showed that the concentrations of PCDD/Fs and DL-PCBs in different sampling methods could be kept within the relative deviation of 10%. Another important work item of the program is to evaluate the timing of the use of the centrifuge and incorporate the results into a draft revision of the sampling methodology. According to laboratory test results, the proposed sampling staff can be assessed by three aspects of the need for the use of centrifuges for surface water or raw wastewater:1.sample sampling volume, 2.concentration of suspended particles in water,3.the amount of water that can be filtered per filter, consideration could be given to incorporating centrifuge equipment to reduce the load on subsequent sampling, so you can shorten the sampling time of 1/3 and save half of the filter paper usage. Through establishment of sampling and analytical techniques for dioxin and polybrominated diphenyl ethers in water under the program, and completion of the investigation on persistent organic pollutants in water, and the establishment of the background database, the reference for environmental protection units in the future revision of sampling methods or regulatory standards development is provided.