Tetrasilasilylone N is composed of a silicon(0) atom, two NHC-coordinated silylenes, and a silaimine (Si=N) group. It reacts rapidly and selectively with the chalcogens selenium and tellurium to afford corresponding dichalcogenides 1 and 2 in high yields of 69-79%. In these compounds, one chalcogen atom is connected to the silicon(0) atom with a short bond in the range of Si=E double bonds. The second chalcogen atom adopts the bridging position between the Si(0) atom and the Si=N group. Using only 1 equiv of tellurium affords the selective formation of monotelluride 3 in 84% yield. In this monotelluride, the tellurium atom adopts a bridging position between the silylone functionality and the Si=N group.