Human breast milk is recommended by World Health Organization as an ideal matrix for conducting human biological monitoring of persistent organic pollutants (POPs). And it is the main matrix to evaluate the efficacy of performing Stockholm Convention. In order to assess the human body burden of POPs and performance evaluation, national monitoring program of breast milk has begun since 2007. Various POPs, including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs), were determined in human breast milk samples. We obtained representative data of levels of main POPs in human breast milk from the general population in China as well as their spatial-temporal distribution, which provided a strong support for the performance evaluation of Stockholm Convention in China.