Microwave-assisted tandem reaction of (Z)-arylvinyl bromides involving an elimination and homocoupling in the presence of DBU and CuI in DMF affords a variety of symmetrical 1, 3- diynes in good to excellent yields. This tandem process, eliminating the need of volatile and savory terminal alkynes, provides an alternative to the conventional homocoupling methods for the synthesis of symmetrical 1, 3-diynes.