Because 6-amino-6-deoxy amylose is an important intermediate for many materials, developing a practical pathway to easily prepare it in bulk is of significance. The synthesis of 6-amino-6-deoxy amylose included three reactions. In the chlorination reaction, the crude product could be fully de-esterified under the improved conditions, and the reaction mechanism was re-understood. The azido group was reduced with sodium borohydride in which the reaction conditions were studied in detail. With the improved synthetic pathway, 6-amino-6-deoxy amylose could be easily prepared. The 6-amino-6-deoxy amylose was characterized via its benzamide derivative with 1 H NMR, 1 H-13 C HSQC NMR, and 1 H-1 H COSY NMR, confirming the hydroxyl group at C 6 of amylose was converted to amino group with a degree of substitution of 98.2%. Additionally, the 6-amino-6-deoxy amylose was analyzed toward iodine reagent and X-ray diffraction, and the corresponding results showed that it was different from amylose in suprastructure and crystal structure.