Copper-promoted direct carbonylation of unactivated sp(3)C-H and aromatic sp(2)C-H bonds of amides was developed using nitromethane as a novel carbonyl source. The sp(3)C-H functionalization showed high site-selectivity by favoring the C-H bonds of alpha-methyl groups. The sp(2)C-H carbonylation featured high regioselectivity and good functional group compatibility. Kinetic isotope effect studies indicated that the sp(3)C-H bond breaking step is reversible, whereas the sp(2)C-H bond cleavage is an irreversible but not the rate-determining step. Control experiments showed that a nitromethyl intermediate should be involved in the present reaction.