The sodium silyl chalcogenolates (NaESiRBU2)-B-t (R = Ph, Bu-t; E S, Se, Te), accessible by the nucleophilic degradation of S, Se, or Te by the sodium silanides (NaSiRBU2)-B-t (R Ph, Bu-t), have been characterized by X-ray structure analysis. Protonolysis of the sodium silyl chalcogenolates yields the corresponding chalcogenols. The Cu and Zn chalcogenolates, [Cu((SSiPhBU2)-B-t)](4) and [ZnCI((SSiBu3)-Bu-t)(THF)](2), have been synthesized by metathesis reactions of CuCl with (NaSSiPhBU2)-B-t and of ZnCl2 with (NaSSiBu3)-Bu-t, respectively. The solid-state structures of the transition metal thiolates have been determined. The compounds (Bu2RSiE)-Bu-t-(ESiRBu2)-Bu-t (R = Ph, Bu-t; E = S, Se, Te) are accessible via air oxidation. With the exception of (Bu3SiS)-Bu-t-(SSiBu3)-Bu-t, these compounds were analyzed using X-ray crystallography and represent the first structurally characterized silylated heavy dichalcogenides. Oxidative addition of (Bu3SiTe)-Bu-t-(TeSiBu3)-Bu-t to Fe(CO)(5) yields [Fe((TeSiBu3)-Bu-t)(CO)(3)](2), which has also been structurally characterized.