alpha-, beta- and gamma-cyclodextrins (CDs) were modified on their secondary face by mechanosynthesis at room temperature using a laboratory scale ball mill. Mono-2-tosylated alpha-, beta- and gamma-CDs were obtained in good yield from mixtures of native alpha-, beta- and gamma-CDs, respectively, N-tosylimidazole and an inorganic base, each of them being in the solid state. The yields appeared to be dependent upon the nature of the base and the reaction time. A kinetic monitoring by 1H NMR spectroscopy demonstrated that the highest yields in mono-2-tosyl-CDs were measured using KOH as a base in very short reaction times (up to 65% in 80 s). Mono-(2,3-manno-epoxide) alpha-, beta- and gamma-CDs were subsequently synthesized by ball-milling a mixture of mono-tosylated alpha-, beta- and gamma-CDs, respectively, and KOH. The characterization of the modified CDs was carried out by X-Ray diffraction, mass spectrometry, solid-state NMR and Diffuse Reflectance UV-Vis (DR UV-Vis) spectroscopies. Clues on the supramolecular arrangement of the molecules in the solid state provide information on the reaction mechanism.