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The flame-retardant polyamide 66 composites (FR-PA66) were prepared by in situ loading of amino-functionalized polyphosphazene microspheres (HCNP), which were synthesized in the laboratory and confirmed by a Fourier transform infrared spectrometer (FTIR), scanning electron microscope (SEM), and transmission electron microscope (TEM). The thermal stabilities and flame retardancy of FR-PA66 were measured using thermogravimetric analysis (TGA), a thermogravimetric infrared instrument (TG-IR), the limiting oxygen index (LOI), the horizontal and vertical combustion method (UL-94), and a cone calorimeter. The results illustrate that the volatile matter of FR-PA66 mainly contains carbon dioxide, methane₄, and water vapor under heating, accompanied by the char residue raising to 14.1 wt% at 600 °C and the value of the LOI and UL-94 rating reaching 30% and V-0, respectively. Moreover, the addition of HCNP decreases the peak of the heat release rate (pHRR), total heat release (THR), mass loss (ML), and total smoke release (TSR) of FR-PA66 to 373.7 kW/m², 106.7 MJ/m², 92.5 wt%, and 944.8 m²/m², respectively, verifying a significant improvement in the flame retardancy of PA66.