202 congeners of chlorobiphenyl (CB) with 109 single-resolved compounds and 93 co-eluting, which represented from mono- to deca-CB were quantified as by-side impurities in all seven and of various type the technical chloronaphthalene (CN) formulations of the Halowax series. IUPAC No. 104, 145, 159, 169, 184, 186, and 188 were undetected (<0.05–<0.7 ng/g). The total CBs content of the Halowax formulations ranged between 220 and 640,000 ng/g, and lower chlorinated Halowaxes 1031 (27% Cl) and 1000 (35% Cl) were two to three orders of magnitude more contaminated with CBs than higher chlorinated Halowax 1001, 1099, 1013, 1014, and 1051 (49–70% Cl). The profile of CB homologue groups of the Halowaxes changed and followed somehow a degree of chlorination of the parent CN mixture. For Halowax 1031 and 1000, a decreasing trend in proportion from mono- to deca-CB was evident, while for Halowax 1001, 1099, 1013, 1014, and 1051 the relative proportions between the CB homologue groups varied somehow. Evidently content of lower chlorinated mono- and di-CBs highly decreased and steadily increased tri- to octa-CBs and they become dominating homologues in Halowax formulations in parallel with an increase of the content of higher molecular weight CN constituents, respectively. Among planar non- and mono-ortho CBs, total concentrations in Halowax formulations were detected in the range of 2.0–2600 ng/g, and only 3,3′,4,4′,5,5′-HxCB (no. 169) was undetected (<0.05 ng/g). Detection of by-side CBs in technical Halowaxes demonstrate clearly that those formulations apart from a massive introduction of dioxin-like CNs become in the past also an early source of environmental pollution with CBs, which proceeded for around 20–30 years use of original CB formulations.