The process for the synthesis of an alkylpolyglucoside having the formula (I):H--(G).sub.n --O--R-- (I)whereinR is linear or branched, saturated or unsaturated C.sub.8 -C.sub.20 alkyl;G is a radical resulting from removal of a molecule of water from a monosaccharide; andn is an integer from 1 to 5;the process entailing reacting an alcohol with a monosaccharide or a compound capable of generating a monosaccharide in in situ, wherein the reaction is carried out in the presence of a catalyst consisting of one or more sterically hindered polyalkylarylsulfonic acids.