Highly halogenated flame retardants (HHFRs) are flame retardants with a halogen content of more than 60% in chlorinated or brominated flame retardants. Due to their high halogen content and excellent flame retardant properties, HHFRs have been widely used in plastics and polymer materials. Compared with conventional flame retardants, HHFRs are more persistent in the environment. At higher concentrations, HHFRs are frequently detected in indoor and outdoor atmosphere and dust, soil, sediments, organisms and even human serum and breast milk, and form more toxic dehalogenation products after degradation. Toxicological evidence shows that HHFRs have significant endocrine disrupting effects, causing neurodevelopmental damage. To scientifically assess and predict the potential environmental and health risks of HHFRs, it is critical to obtain accurate and reliable qualitative and quantitative data. However, due to the high boiling point of HHFRs and their easy dehalogenation under photothermal effect, the analysis of trace HHFRs in complex environmental matrices is still challenging, which hinders the in-depth understanding of their environmental behavior and toxicity mechanism. The recent advances in sample pretreatment and instrumental analysis of several typical HHFRs at home and abroad, such as decabromodiphenyl ether (BDE-209), decabromodiphenyl ethane (DBDPE), dechlorane plus (DP), tetrabromobisphenol A/S derivatives (TBBPA/S-DBPE), 2,4,6-tris (2,4,6-tribromophenoxy)-1,3,5-triazine (TTBP-TAZ) and tris (tribromoneopentyl) phosphate (TTBNPP), were summarized, and their physical and chemical properties and environmental occurrence characteristics were reviewed. The advantages and disadvantages of the current analytical methods were sorted out, and the future research directions were prospected.