The present invention provides a simplified process for preparing surface active glycoside mixtures such as the C8-C22 alkyl glycosides directly from hydrophilic saccharide-containing compositions by fatty alcohol interchange. The lipophilic fatty alcohol and hydrophilic saccharide-containing compositions are rendered reactively compatible with one another by incorporating into the reaction medium a sufficient amount of nonionic surface active agent (e.g. long-chain organo glycoside) to permit the fatty alcohol interchange.; Long chain-alkyl glycoside mixtures can be easily prepared under acid catalysis and elevated temperatures for either dextrose or lower alkyl glycoside mixtures by direct fatty alkyl alcohol interchange by means of reaction medium which contains a sufficient amount of long-chain alkyl glycoside to render these normally incompatible reactants reactively compatible with one another. Relatively small amounts of nonionic surface active reagents (e.g. 0.2 moles for each mole of anhydrous glucose unit) have been found to significantly increase fatty glycoside mixture yields under the processing conditions of this invention.