AbstractWe report the development of a new methodology for the preparation of cyclic tetrasubstituted alkenes with π‐conjugated substituents. The synthesis of the target compounds was accomplished through the regioselective cross‐coupling reaction of diphenyl bromocyclohexenyl phosphate with organozinc reagents. The procedure succeeded in the preparation of alkenes with two pyrene moieties. The absorption and photoluminescence spectra of the prepared compounds were measured.