NADFP·DMF has good detonation performance, mechanical sensitivity and high thermal decomposition temperature. Current studies on NADFP·DMF have been carried out at ambient temperature and pressure, and its properties under pressure have yet to be analysed in depth. By using the generalized gradient approximation (GGA) plane-wave norm conserving pseudopotential method based on the framework of density functional theory, the structural, mechanical, electronic and thermodynamic properties of the monoclinic crystal system NADFP·DMF under 0–20 GPa are calculated. The calculations show that the lattice parameters decrease with increasing pressure. The structure is mechanically stable and ductile within 0–20 GPa. We analyzed electronic properties, including band structure and density of states. NADFP·DMF is a direct band gap compound only at 15 GPa, and the band gap decreases with increasing pressure, resulting in an increase in sensitivity. In addition, the thermodynamic properties of NADFP·DMF are investigated, including enthalpy, temperature*entropy, Gibbs free energy, Debye temperature and heat capacity.