In this paper, the thermal decomposition behavior of 3,5-difluoro-2,4,6-trinitroanisole (DFTNAN) was studied by differential scanning calorimetry (DSC) and thermogravimetry (TG) by using different heating rates (2, 5, 10, 15 °C·min⁻¹). Subsequently, the kinetic and thermodynamic parameters of non-isothermal thermal decomposition of DFTNAN were calculated. The critical temperature of thermal explosion ($T_{\mathrm{b}}$) and self-accelerating decomposition temperature ($T_{\mathrm{ASDT}}$) were determined to be 249.03 °C and 226.33 °C, respectively. The compatibility of DFTNAN with a number of high explosives (cyclo-1,3,5-trimethylene-2,4,6-trinitramine (RDX), 1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaaza-tetracyclo-[5.5.0.05,9.03,11]-dodecane (CL-20) and dihydroxylammonium 5,5’-bistetrazole-1,1’-diolate (TKX-50)) was studied at different mass ratios using DSC. The criteria to judge the compatibility between the materials were based on a standardization agreement (STANAG 4147). The thermodynamic study results revealed that DFTNAN possessed superior thermal safety and stability. The experimental of compatibility results indicated that the mass ratios of the high explosives in the DFTNAN/RDX, DFTNAN/HMX and DFTNAN/CL-20 compositions more than 40%, 60% and 70% exhibited good compatibility, whereas DFTNAN/TKX-50 demonstrated poor compatibility.