Very little is known about mixed polybrominated/chlorinated dibenzo-p-dioxins and dibenzofurans (PBCDD/F) in industrial thermal processes. In this study, the occurrences and characteristics of PBCDD/F from various incineration and metallurgical processes were investigated. In addition, PBCDD/F analytical protocols based on HRGC/HRMS were developed and optimized. The sum of isomer group concentrations ranged from 1.7-3740 pmol Nm(-3) for PBCDF and 0.2-582 pmol Nm(-3) for PBCDD. For some metallurgical industries, the amounts of PBDD/F and PBCDD/F emitted were similar to or even higher than the amounts of PCDD/F. The sources of bromine and brominated-precursors in these processes should be evaluated. The PBCDD/F characteristics investigated included isomer group patterns, ratio of bromine and chlorine incorporated in PBCDD/F, and ratio of halogenated furans to dioxins. Lower brominated PBCDD/F were binomially distributed. But in some cases, the concentrations of higher brominated PBCDD/F were much higher than predicted from the binomial distribution. The formation mechanisms of PBDD/F, PBCDD/F, and PCDD/F in these processes were also evaluated.