A novel methodology for the rapid synthesis of 11 1-chloro-2-arylcyclohexenes in 89-95% yields, employing the regioselective Suzuki-Miyaura cross-coupling reaction, under microwave conditions in aqueous media is reported. The products formed in less than 7 minutes duration. The crystal structures of two representative compounds of 1-chloro-2-arylcyclohexenes, with biphenyl- and naphthyl- substituents have been analyzed. The compounds crystallized in the monoclinic system with P2(1)/n and P2(1) space groups, respectively, and are stabilized by two weak interactions C-H center dot center dot center dot Cl and C-H center dot center dot center dot Cg.