In azidic binders for solid propellants, the N3 functionality is introduced by substitution of a halogen or tosyl group, but recently the mesyl group has been suggested as an alternative. The mesylate group has two advantages, mainly related to its small dimensions and low cost. Poly(glycidyl azide) and poly 3-azidomethyl-3-methyl oxetane were prepared by using both tosylate and mesylate precursors. The azidation kinetics were studied at three different temperatures while keeping all other operating parameters the same. The results confirmed the good potential of the mesylate precursors for the production of azidic binders.