An efficient methodology for the synthesis Or unsymmetrical biheteroaryl molecules has been developed via Pd(II)-catalyzed oxidative C-H/C-H cross-coupling, of heteroarenes. An inversion in reactivity and selectivity has been achieved successfully to perform the desired heterocoupling. This process allows the heterocoupling of not only electron-rich N-containing, heteroarenes (e.g., xanthines, azoles, and indolizines) but also electron-poor pyridine N-oxides with various thiophenes or furans.