For the first time the structurally characterized heavier chalcogen analogues of alkanoyl halides,[{HC(CMeNAr)(2)}Ge(S)X] (Ar = 2,6-iPr(2)C(6)H(3); X = Cl (1), F (2)) and [{HC(CMeNAr)(2)}Ge(Se)X] (X = Cl (4), F (5)) have been prepared from the starting material [{HC(CMeNAr)(2)}GeCl] (3). The nature of the germanium-chalcogen bond is best described as between the two resonance structures, Ge+-E- <-> Ge=E. The investigation of the reactivity of the germanium-halogen bond with RLi reagents (R = Me, nBu) led to the formation of [{HC(CMeNAr)(2)}Ge(E)R] (E = S, R = Me (6); E = Se, R = Me (7), nBu (8)). The solid-state structures of 1, 2, 4, 5, 6, and 8 are reported.