Silanes possess unique physicochemical properties because of five empty 3d orbitals in their silicon atoms. However, traditional synthesis methods for functional silanes are tedious, costly, and feature low conversion rates. In this work, diverse functional silanes were accurately synthesized with simple and efficient routes, and they were further applied to synthesize nanomaterials. The syntheses were performed in simple vials by utilizing thiol and alkene or alkyne silanes as raw materials at a 1:1 or 2:1 ratio of thiol to unsaturated silanes, respectively. Structures and photophysical properties of obtained products were thoroughly characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance, liquid chromatography–mass spectrometry, and fluorescence spectrophotometry. A series of silicon‐containing products were synthesized to enrich the library of silicon‐based materials, and a fundamental research was conducted to understand reactions and product characters. 2‐((3‐(Trimethylsilyl)propyl)thiol)succinic acid (Te‐3) was selected as starting molecule to coordinate with lanthanide ions, and coordinate complexes formed regular nanorods, with some forming branched structures and showing strong luminescence of lanthanide ions. Novel aggregation of Te‐3 complexes was characterized and discussed. This work benefits understanding and preparation of metal–organic complex nanomaterials.