6.5 g (5.0 mmol) of mono-6-OTs--CD was dissolved in 15 mL of dry DMF and stirred at room temperature until completely dissolved, then sodium azide (0.4 g, 6.15 mmol) was added and the reaction was carried out under nitrogen protection at 75 for 10 h. After the reaction was finished and cooled down to room temperature, the reaction solution was slowly added into 300 mL of acetone and stirred for 30 min, and then filtered. After stirring for 30 min, the filter cake was extracted and dried under vacuum to obtain a white powder, i.e., mono-6-O-(azido)--cyclodextrin, 5.0 g, with a yield of 85.1%.