A cerium-catalyzed C-H alkylation of N-sulfonyl ketimines with low-cost and readily available alkanes as alkyl sources was developed. This transformation proceeded through the synergy of photoinitiated ligand-to-metal charge transfer (LMCT) using a chlorine radical as an HAT reagent and air as a green oxidant. A series of alkylated N-sulfonyl ketimines were synthesized with moderate to good yields in a highly atom-economic manner under chemical oxidant-free conditions.