Methods toward the dimerization and homocoupling of terminal alkynes have been established that employ Co complexes along with tBuOK under different atmosphere. A variety of Z‐1,3‐enynes were furnished with a high Z:E (up to 93:7) ratio in moderate to very good yields under inert atmosphere. Alternatively, the Glaser homocoupling reaction of terminal alkynes was also accomplished with a Co catalyst, successfully affording various 1,3‐diynes in excellent yields (up to 93 %) under oxygen.