Analytical methods based on gas chromatography in combination with electron capture negative ion/electron ionisation mass spectrometry were developed and validated for the separation and determination of legacy and emerging flame retardants (EFRs) in a wide range of samples including indoor air, dust, diet and human milk. A broad suite of EFRs and legacy flame retardants (FRs) including polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDDs) were determined in indoor air and dust taken from offices and homes in Birmingham, UK. Comparison with previous data, suggests that temporal trends in contamination with EFRs and legacy FRs reflect changes in production and use of such compounds as a result of bans and restrictions on the use of legacy FRs. Using inter alia a simple, single compartment, steady state pharmacokinetic model, human exposure to FRs via air inhalation, dust ingestion and diet was estimated for different age groups and the relative importance of each exposure route to overall exposure assessed under different exposure scenarios. Concentrations of target EFRs were detected for the first time in UK human milk samples (n=35). Human exposure to EFRs and HBCDDs via diet was estimated for a population impacted by a rudimentary e-waste processing area in Vietnam.