The efficient, simple, and environment-friendly route of direct cyanation of picolinamides has been developed with nontoxic K-4[Fe(CN)(6)] as the cyanide source through Pd-catalyzed C-H bond activation. A series of N-(naphthalene-1yl)picolinamide derivatives were successfully transformed to the corresponding cyanation products. The cyanation mechanism has also been speculated.