AbstractA reaction of nitrones with 1,2‐dibromotetrafluoroethane affording bromodifluoroethyl‐substituted hydroxylamines is described. The process is performed in the presence of a ruthenium photocatalyst and ascorbic acid as a stoichiometric reducing agent and is mediated by blue light irradiation. The fluroalkylation products can undergo chemoselective transformations involving either N−O or C−Br bonds furnishing various tetrafluorinated compounds.magnified image