In the current work, a synergistic flame retardant based on phosphate-functionalized silica (PhosFS) has been synthesized by utilizing alkyne−azide click chemistry between 2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane, 4-(azidomethyl)-1-oxide, and propargyl-functionalized silica (PFS). Phosphate-functionalized silica was characterized using various techniques such as solidstate 31 P nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis, and inductively coupled plasma−mass spectrometry. PhosFS, when incorporated into thermoplastic polyurethane (TPU), showed superior thermal stability and higher char yield in comparison with TPU. The flammability of the composites was analyzed by UL-94 vertical burning and limiting oxygen index (LOI) test. With the addition of 10 wt % PhosFS in TPU, the LOI value increased to 28.5% and the V-0 rating was achieved by UL-94. The plausible mechanism for the flame retardance property of composites has been proposed on the basis of results obtained from FTIR and scanning electron microscopy−energy dispersive X-ray spectroscopy. TPU composites based on phosphate-functionalized silica exhibited better flame retardancy due to the formation of continuous and highly entangled char.