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C–F/C–H functionalizations proved to be viable within a versatile manganese(I) catalysis manifold. Thus, a wealth of fluorinated alkenes were employed in C–F/C–H functionalizations through facile C–H activation. The robust nature of the manganese(I) catalysis regime was among others reflected by the first C–F/C–H activation with perfluoroalkenes as well as racemization-free C–H functionalizations on imines, amino acids, and peptides.