Sequential thiol-ene click reaction is reported for amphiphilic glycosylated polyphosphazene. Poly [bis(allylamino)phosphazene] was used as precursor to go through UV irradiation with 2,3,4,6-tetra-O-acetyl-1-thiol-beta-D-glucopyranose (SH-GlcAc(4)) and 1-dodecanethiol in sequence. Variation of the reaction conditions, including click reaction time and the dose of photoinitiator, led to different hydrophilic/hydrophobic ratios. As a result, glycosylated polyphosphazenes were synthesized with 533%, 77.7% and 85.0% of glucose moieties. The different residual composition could give rise to different self-assembly behaviors. Micelles of amphiphilic polyphosphazenes were formed in aqueous solution and the CMC value (0.79 x 10(-3)-4.00 x 10(-3) mg/mL) as well as mean diameter (170-220 nm) varied along with the hydrophilic glucose moiety/hydrophobic dodecyl moiety ratio. (C) 2014 Elsevier Ltd. All rights reserved.