Hydrosilylation of a wide group of alkynes (terminal and internal) with four structurally different silanes has been for the first time performed in supercritical CO2 (scCO(2)). The results clearly showed the advantages as well as the limitations of using of scCO2 as a reaction and extraction medium for hydrosilylation of numerous alkynes with different functionality and volatility. Procedures for the synthesis and isolation of over forty silyl ethenes were described, among which more than twenty for the first time. Obtained products were fully characterized by H-1, C-13, Si-29 NMR, GC-MS, and EA. Moreover, by X-ray crystallography, the molecular structures of (E)-3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-y1)-2,5-dimethylhex-3-ene2,5-diol (3n) and (E)-triethyl(2-(triphenylsilyl)vinyl)silane (12a) have been determined for the first time. (C) 2017 Elsevier Inc. All rights reserved.