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Reactions of 1,3-ketoesters, -diesters, -diketones, and -ketoamides with [Me4N][SeCF3] into the existence of the right oxidant supplied a series of 2-trifluoromethylselenolated 1,3-dicarbonyls in reasonable to good yields. The trifluoromethylselenolation featured simplicity, mildness, large efficiency, transition-metal-free conditions, and compatibility of various oxidants, and represented initial oxidative trifluoromethylselenolation of 1,3-dicarbon