C–H and C–N bonds in tertiary amines were activated by the germanium­(IV) corrole cation [(TPFC)­Ge]+ (TPFC = 5,10,15-tris­(pentafluorophenyl)­corrole) at room temperature. Cleavage of C–H bonds with a unique selectivity for the β- and γ-positions in tertiary amines was observed, in contrary to the well-studied α-position selectivity in C–H bond cleavage promoted by transition-metal compounds. Preliminary mechanism studies using density functional theory (DFT) calculation indicated a nucleophilic substitution pathway for C–N bond activation. Although the mechanism for the C–H bond activation was not clear at the present stage, a cooperative Lewis acid/base reaction pathway was also calculated.