Herein, the combined application of characterization tools, such as Raman spectroscopy, thermal gravimetric analysis coupled with mass spectrometry, and optical and atomic force microscopy, confirms the reductive silylation of synthetic carbon allotropes as a new covalent functionalization strategy for the formation of heteroatom-carbon bonds. In particular, our study gives interesting insights into the topology-driven retrofunctionalization of nanotubide and graphenide derivatives.