Polybrominated diphenyl ethers (PBDEs) have been used as flame retardants in a variety of materials and products. PBDEs have been shown to accumulate in the environment and human populations while exhibiting a range of toxic effects. In this study, surface soil samples from 30 sites in the city of Melbourne, Australia, were analysed for PBDEs. Eight congeners of environmental concern (BDE-28, -47, -99, -100, -153, -154 -183 and -209) were assessed using selective pressurized liquid extraction (S-PLE) and gas chromatography coupled to triple quadrupole mass spectrometry (GC-MS/MS). PBDEs were detected in 29/30 samples with Σ8PBDE soil concentrations ranging nd-13,200 ng/g dw and Σ7PBDEs (excluding BDE-209) levels of nd-70.5 ng/g dw. Soils from waste disposal sites (n = 6) contained the highest median Σ7PBDE and Σ8PBDE concentrations, followed by manufacturing sites (n = 18) and then non-source sites (n = 6). Electronics recycling facilities contained the greatest levels of Σ8PBDEs by a significant margin (p < 0.05) to indicate that these industries are a potential source of contamination. BDE-209 was the dominant congener, contributing an average of 75.5% to Σ8PBDEs soil concentrations, followed by BDE-47, BDE-99 and BDE-183 at 7.90, 5.64 and 4.31%, respectively. Congener profiles reflected global estimates of Deca-BDE, Octa-BDE and Penta- BDE commercial production, with the most significant congener correlation existing between BDE-47 and BDE-99 (p < 0.001, r = 0.943). This first assessment of PBDEs in Melbourne soils indicates widespread contamination of the urban environment, including locations where direct sources to soil are not clear.