A palladium-catalyzed interannular C-H amination of biaryl amines with O-benzoylhydroxylamines is reported. This reaction undergoes smoothly with operational practicality and good tolerance of functional groups, thereby providing a concise synthesis of 2,2'-diaminobiaryls. Moreover, the readily accessible scale-up synthesis and the ability to transform the products into structurally diverse N-containing heterocycles demonstrate the synthetic potential of this catalytic protocol.