In order to study the effect of the electric field on the propellant in the process of hydroxylamine nitrate-based liquid propellants electric ignition, geometry and charge distribution of NH3OH+ were optimized using density functional theory (DFT)/B3LYP at 6-311++G(d, p) basis set level under different external electric field. Vertical ionization potential, adiabatic ionization potential, energy levels and HOMO-LOMO gap were calculated. And H+-loss dissociation reaction of NH3OH+ was studied. The results show that the geometry, charge distribution and ionization potential are obviously dependent on electric field intensity. In the negative direction, with the increasing of the electric field intensity, the energy gap and dissociation reaction barrier are proved to decrease. And the dissociation of NH3OH+ is becoming easier to occur.