Halogen-free organophosphorus flame retardants have promising application prospects due to their excellent safety and environmental protection properties. A cobalt-coordinated cyclic phosphonitrile flame retardant (Co@CPA) was synthesized via a hydrothermal method using hexachlorocyclotriphosphonitrile (HCCP), 5-amino-tetrazolium (5-AT), and cobalt nitrate hexahydrate (Co(NO )2∙6H O) as starting materials. The structure was characterized using Fourier transform infrared (FTIR), nuclear magnetic resonance spectroscopy (1H-NMR), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). Thermoplastic polyurethane (TPU) composites were prepared by incorporating 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphame-10-oxide (ODOPB), Co@CPA, and silicon dioxide (SiO ) via melt blending. The flame-retardant performance and thermal stability of the TPU composites were evaluated through limiting oxygen index (LOI), vertical combustion (UL-94), TG, and cone calorimetric (CCT) tests. SEM and Raman spectroscopy were used to analyze the surface morphology and structure of the residual carbon. A synergistic flame-retardant effect of ODOPB and Co@CPA was observed, with the most effective flame retardancy achieved at a TPU:ODOPB:Co@CPA:SiO ratio of 75:16:8:1. This composition exhibited an LOI value of 26.5% and achieved a V-0 rating in the UL-94 test. Furthermore, compared to pure TPU, the composite showed reductions in total heat release, CO production, and CO production by 6.6%, 39.4%, and 48.9%, respectively. Our research findings suggest that Co@CPA demonstrates outstanding performance, with potential for further expansion in application areas. Different metal-based cyclic phosphonitrile compounds are significant in enriching phosphorus-based fine chemicals.