For the first time, 2-O-methyl- (2MC) and 3,6-di-O-methyl-cellulose (36MC) were synthesized via 3-O-allyl- and 3-O-methyl-cellulose, respectively. Position 6 of 3-O-allyl- and 3-O-methyl-cellulose was protected with the 4-methoxytrityl groups. The reaction time and temperature were optimized to achieve a high regioselectivity at C-6 and to prevent the introduction of the 4-methoxytrityl group at C-2 of the polymer. It was found that the substituent at C-3 of 3-O-functionalized celluloses influenced the reactivity of the hydroxyl group at C-6. The structure was characterized by means of H-1 and C-13 NMR spectroscopy of the acetates of 2MC and 36MC. 2MC and 36MC were soluble in water and did not show thermoreversible gelation.