A highly efficient nickel/silver co-catalyzed C–H amination at the C5 position of 8-aminoquinolines with azodicarboxylates at room temperature is reported. The reaction undergoes a self-redox process without the necessity of external oxidant. It proceeded under simple and mild conditions without any additional ligand, base or oxidant and provided the desired products in good to excellent yields. This method also possessed the merits of good functional group compatibility and air and moisture tolerance. It provides an efficient strategy for the synthesis of useful quinoline derivatives.