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The pronounced electron\u2010withdrawing effect of the pentafluoroethyl group leads to a markedly increased Lewis acidity at the central atom which results in the stabilization of hypervalent complexes, anionic element(II) species as well as remarkable reactivities of element\u2010element and element\u2010hydrogen bonds. By addition to unsaturated C\u2212C bonds or by reaction with organic halides as well as transition\u2010metal complexes the molecules bearing a pentafluoroethyl\u2010element group are readily accessible. Moreover, the utilization of pentafluoroethyl groups facilitates the formation of donor\u2010stabilized germylenes and stannylenes. A series of such compounds serves as suitable pentafluoroethylation reagents. 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