Cellulose, as one of the most abundant natural biopolymers, has been widely used in textile industry. However, owing to its drawbacks of flammability and ignitability, the large-scale commercial application of neat cellulose is limited. This study investigated some TEMPO-oxidized cellulose (TOC) which was prepared by selective TEMPO-mediated oxidation and ion exchange. The prepared TOC was characterized by Fourier transform infrared (FT-IR) spectroscopy and solid-state 13C-nuclear magnetic resonance (13C-NMR) spectroscopy. The thermal stability and combustion performance of TOC were investigated by thermogravimetry analysis (TG), microscale combustion calorimetry (MCC) and limiting oxygen index (LOI). The results demonstrated that the thermal stability of TOC was less than that of the pristine material cellulose, but the peak of heat release rate (pHHR) and the total heat release (THR) of all TOC were significantly reduced. Additionally, the LOI values of all TOC products were much higher 25%. In summary, the above results indicated that the modified cellulose with carboxyl groups and metal ions by selective oxidation and ion exchange endows efficient flame retardancy.