The acid-catalysed mechanism of the reaction using trifluoromethanesulfonic anhydride to synthesize symmetrical 1,1′-glycosyl-glycosides such as trehalose and galacto, manno, arabino, xylo etc. analogues has been elucidated. The authors were able to prove by 19F nmr study at low temperature that the efficiency of the system is due to the peculiar property of trifluoromethanesulfonic acid generated in situ to form a stable, insoluble hydroxonium trifluoromethanesulfonate CF3SO3− H3O+. The procedure satisfies the two necessary conditions for a glycosylation reaction being workable: (i) the presence in catalytic amounts of free acid which is regenerated during the condensation step; (ii) a very efficient trapping of the water liberated during the protonation step which displaces the equilibrium towards the formation of the glycoside. The α-stereoselectivity of the reaction is discussed in terms of anomerisation of the β-anomers on to the thermodynamically more stable α ones, through a cyclic oxonium intermediate.