Vinyl ethers, promising chiral carbohydrate synthons, have been synthesized by the addition of glucose acetals (1,2:5,6-di- O-isopropylidene-α- d-glucofuranose, methyl 4,6- O-benzylidene-α- d-glucopyranoside, 1,2- O-cyclohexylidene-α- d-glucofuranose, methyl α- d-glucopyranoside) to acetylene under atmospheric and elevated pressures in an autoclave in the presence of superbase catalytic systems (KOH–DMSO, t-BuOK–DMSO). The complete vinylation of 1,2:5,6-di- O-isopropylidene-α- d-glucofuranose and methyl α- d-glucopyranoside has been realized under elevated pressure of acetylene in the system KOH–THF as well.