Persistent organic pollutants (POPs) are of global concern due to their negative effects on humans and the environment, and globally are regulated in the Stockholm Convention on POPs. The present study had Mongolia as a partner in a multinational project funded and coordinated by the United Nations Environment Programme with the aim to monitor POPs in core media, including air (with passive samplers), water, and a pooled human milk sample. Project implementation and all sampling were undertaken by the Institute of Chemistry and Chemical Technology whereas POPs analysis was performed in laboratories abroad. Brominated and chlorinated POPs were analyzed by gas chromatography/mass spectrometry, perfluorinated compounds (PFAS) and isomers of hexabromocyclododecane (HBCD) by liquid chromatography/mass spectrometry. The monitoring results found very low concentrations of PFAS in river water. Toxic equivalents (TEQs) for PCDD/PCDF were low in air and in human samples but had a relatively higher presence of TEQ from dioxin-like PCB than in other countries. With respect to chlorinated POPs, drins, chlordanes, DDTs, heptachlors, and mirex were very low in air and human milk. Elevated levels were found for polychlorinated biphenyls (PCB), hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs), pentachlorobenzene (PeCBz), and HBCD in air with extreme values for hexachlorobutadiene. The abundance of HCHs and HCB was confirmed in the human milk sample but not for PCB, PeCBz or HBCD. Short-chain chlorinated paraffins (170 ng/g lipid) were the highest among all human milk pools. It is recommended to continue POPs monitoring in the future, especially for those where high concentrations were found. •Mongolia's first contribution to the global monitoring plan of POPs.•Legacy industrial POPs (PCB, HCB, HCH) were more abundant than organochlorine pesticides.•Perfluorinated POPs were very low in water, and comparatively low in air and humans.•High concentrations of SCCP in human milk and HCBD in air need confirmation.