A novel synthetic strategy was developed to prepare polyphosphazenes containing C,, moieties as side chains. Thus, a new reactive macromolecular intermediate, polyphosphazene azides (P1), was obtained from poly(dichlorophosphazene) by the direct nucleophilic substitution reaction. Then the azide group in P1 reacted with C,, molecules to afford the first example of C-60-containing polyphosphazenes (P2 and P3). The polymers are soluble in common organic solvents. Molecular structural characterization for the polymers was presented by H-1 NMR, C-13 NMR, IR, ultraviolet-visible spectra, and gel permeation chromatography. (C) 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 194-199, 2004.