Described herein is a dual chelation-assisted RhCl3-catalyzed oxidative C-H/C-H cross-coupling reaction of aniline derivatives. The highlight of this methodology is the chemo- and regioselective cross-coupling between electronically similar substrates, which represents a highly challenging task in oxidative Ar-H/Ar-H cross-coupling reactions. Furthermore, this Cp*-free catalytic reaction tolerates a range of functional groups and requires only a low molar ratio of coupling partners. These features expedite the synthesis of unsymmetrical 2,2'-diaminobiaryls.