The dehydrogenative cross-coupling (CDC) reaction of diversely substituted azoles, synergistically catalyzed by copper and cobalt, is reported. This protocol represents the first example of the use of air as an oxidant to carry out this chemical reaction. The process provides a convenient and economical method for the construction of valuable unsymmetrical bis-heteroaryl compounds, including bis-benzoazole compounds that were not obtained in previous catalytic CDC reactions.