A simple and efficient protocol for silver(I)-catalyzed picolinamide directed C4-H amination of 1-naphthylamine derivatives with readily available azodicarboxylates has been developed, demonstrating a new approach to 1,4-naphthalenediamine derivatives in high yields. Note that this reaction system could proceed under external-oxidant- and additive-free conditions (only requires 5 mol % of AgOAc as the catalyst in acetone).