Behavior of Br in pyrolysis of the printed circuit board waste with valuable copper and oil recycling has been studied in the present work. Experimentally, pyrolysis of the printed circuit board waste generated approximately 40.6% of oils, 24.9% of noncondensible gases and 34.5% of solid residues that enriched in copper (90–95%). The cuts of the oils produced from pyrolysis of the printed circuit board waste into weighted boiling fraction were primarily light naphtha and heavy gas oil. Approximately 72.3% of total Br in the printed circuit board waste were found in product gas mainly as HBr and bromobenzene. However, by extended X-ray absorption fine structural (EXAFS) spectroscopy, Cu–O and Cu–(O)–Cu species with bond distance of 1.87 and 2.95 Å, respectively, were observed in the solid residues. Essentially, no Cu–Br species was found.