Amphiphilic graft polyphosphazenes (EtTrp/PNIPAni-PPP) with different mole ratios of hydrophobic groups to hydrophilic segments were synthesized by ring-opening polymerization and Subsequent substitution reactions. The self-assembly behavior of these graft copolymers was studied in detail by TEM, SEM, CLSM, and AFM. Depending on the copolymer composition and common organic solvent employed in dialysis process, supramolecular aggregates ranging from network, nanospheres, high-genus particles to macrophage-like aggregates were produced with graft copolymers.