Hydroxylated (OH-), methoxylated (MeO-), diOH-, OH-MeO-, and diMeO-polybrominated diphenyl ethers (PBDEs) are compounds present in the marine environment. OH-PBDEs are of toxicological concern and are therefore of interest to monitor in the environment. A phenolic octaBDE was tentatively identified in the phenolic fraction of previously analysed mussel samples after methylation of the halogenated phenolic compounds (HPCs). The aim of the present study was to confirm the identity of this compound in blue mussels and investigate whether the analyte is diOH- and/or OH-MeO-octaBDE. Two reference standards, i.e. 6,6’-dimethoxy-2,2’,3,3’,4,4’,5,5’-octabromodiphenyl ether (6,6’-diMeO-BDE194) and 6-ethoxy-6’-methoxy-2,2’,3,3’,4,4’,5,5’-octabromodiphenyl ether (6-EtO-6’-MeO-BDE194) were prepared via O-arylation of 2,3,4,5-tetrabromo-6-methoxyphenol and 2,3,4,5-tetrabromo-6-ethoxyphenol, respectively, with a novel unsymmetrical diaryliodonium salt, 2,3,4,5-tetrabromo-6-methoxydiphenyliodonium triflate. The GC retention time and GC/MS spectrum of the synthesised 6,6’-diMeO-BDE194 correspond well with the analyte in the methylated phenolic fraction of a mussel extract from a previous study. Structural analysis performed in this study indicate that the synthesised 6,6’-diMeO-BDE194 and 6-EtO-6’-MeO-BDE194 correspond well with 6-hydroxy-6’-methoxy-2,2’,3,3’,4,4’,5,5’-octabromodiphenyl ether (6-OH-6’-MeO-BDE194) after methylation and ethylation, respectively, of the HPCs in the mussel extracts. The 6-OH-6’-MeO-BDE194 was identified and quantified in new mussels, sampled in 2012 from two locations on the Swedish west coast, with mean concentrations of 4200 and 430 ng/g fat, respectively.