Abstract: Oxyalkylene group of an alkylene oxide is inserted into a chain-type ether compound having at least one lower alkyl group by reacting the latter with the alkylene oxide in the presence of a catalyst prepared by mixing boron trifluoride and/or stannic chloride with an active-hydrogen compound exemplified by water or a lower aliphatic alcohol. The reaction results reduced formation of by-product dimer of the alkylene oxide even under an increased charging ratio of the alkylene oxide to the chain-type ether.