Intramolecularly‐stabilized germanium, tin, and lead alkoxides of the type M(OCH2CH2NR2)2 [R = Et, M = Ge (1); R = Me, M = Sn (2); R = Me, M = Pb (3)] are suitable precursors for the synthesis of group 14 chalcogenides ME (M = Ge, Sn, Pb; E = S, Se, Te) in scrambling reactions with (Me3Si)2S and (Et3Si)2E (E = Se, Te) at moderate temperatures via hot injection method. The reactions proceed with elimination of the corresponding silylether as was proven by in situ 1H NMR spectroscopy. The solid‐state structures of the homoleptic complex 1 and the heteroleptic complex ClGe(OC2H4NEt2) (4) were determined by single‐crystal X‐ray diffraction, whereas the group 14 chalcogenides were characterized by XRD, SEM, and EDX.