Even though 2,2’-diiodo- and 2,2’-dibromobiaryls represent accomplished precursors for heterofluorenes and other extended π-conjugated systems, their preparation still remains nontrivial when structural diversity of the biaryl backbone is required. Herein, we report a convenient method for the preparation of various 2,2’-diiodobiaryls from 2- iodobiaryls via cyclic diaryliodonium intermediates. An iodinative ring-opening of the diaryliodonium salts, mediated by a copper/diamine catalyst system, is able to afford the corresponding 2,2’-diiodobiaryls under mild conditions. The versatility of this two-step approach is demonstrated by the preparation of hitherto unexplored tetraiodoteraryls and their conversion into ladder-type π-conjugated systems.