AbstractMethyl mono‐ and methyl di‐O‐allyl‐α‐D‐glucosides are prepared by the reaction of methyl α‐D‐glucoside with allyl chloride in alkali in a two‐phase system. The monoallyl ether consists mainly of a mixture of methyl 2‐, 4‐, and 6‐O‐allyl‐α‐D‐glucosides, the diallyl compound of 2,6‐ and 4,6‐di‐O‐allyl‐α‐D‐glucosides in approximately a 1 : 1 ratio. Both compounds are homopolymerized with oxygen as the catalyst. The poly(monoallyl glucoside) is a water‐soluble, brittle, clear resin with a softening point of 100–110°C. The poly(diallyl glucoside) is a brittle, clear, but completely insoluble resin with no softening point. Copolymerization with acrylamide under certain conditions yields water‐soluble polymers, aqueous solutions of which exhibit high viscosities and have the typical appearance and consistencies of those of polysaccharides.