The effect of an amine catalyst on oxyalkyalation of alcohols of low relative molecular mass was studied. The reactivity and selectivity of the formation of the first homologues depend upon the alcohol, the alkylene oxide and the degree of oxyalkylation and decrease in the following order methanol > ethanol > butanol > 2-methylpropanol. The formation of the first homologue is significantly more selective in oxypropylation in comparison to oxyethylation. Triethylamine used as the catalyst undergoes by-reactions giving N,N-diethylethanolamine and then oxyethylated diethylamines which exhibit catalytic activity.