Several studies have indicated that mixed brominated/chlorinated organic compounds could be formed during the thermal process such as the incineration of municipal solid waste and open burning of unregulated e-waste at recycling areas. In this study, air particles and soils from e-waste recycling areas, as well as outdoor and indoor air particles from urban Guangzhou, were collected and pooled for the identification of mixed chlorinated/brominated diphenyl ethers (PXDEs). Three monochloro-nonabromo diphenyl ethers (Cl-nonaBDEs), including 6'-Cl-BDE-206, 5'-Cl-BDE-207, and/or 4'-Cl-BDE-208, were first structurally identified in these air and soil samples. The identification was done by comparison of retention times in chromatograms of pure reference compounds and environmental samples, as well as by comparison with full-scan mass spectra data in electron capture negative ionization mode. Because of their similar physical-chemical properties, 4'-Cl-BDE-208 and 5'-Cl-BDE-207 absolutely coeluted, even on a nonpolar DB-5 column. Further investigation is still needed to clarify these findings. Nevertheless, the results indicated that Cl-nonaBDEs would occur in various environmental matrices. Because the replacement of Br by Cl will change the physical-chemical properties of PBDE analogues, environmental occurrence, fate, and transport, the potential toxicity of PXDEs should be investigated.