The structural phase transition, electronic properties, and bonding properties of antimony nitrides have been studied by using the first principles projector augmented wave method. The relationship between the formation enthalpy and the composition of the Sb-N system has been explored. The novel Sb 2 N 3 with the Cmcm space group is stable in a narrow pressure range from 100 GPa to 120 GPa. Apart from the Sb 2 N 3 , two nitrogen-rich phases SbN 2 and SbN 4 were predicted. The SbN 2 with the C 2/ m space group is stable at 12 GPa and then transforms to the high-pressure phase at 23 GPa. The nitrogen-rich SbN 4 appears at 14 GPa then undergoes C 2/ m → P 1̄ → P 1̄ phase transitions, and the calculated pressures of the phase transitions are 31 and 60 GPa, respectively. The nitrogen-rich SbN 2 and SbN 4 have similar structural features. Both SbN 2 and SbN 4 can be seen as a sandwich structure composed of the Sb-N layers and N 2 dimers. The pressure-induced phase transitions of SbN 2 and SbN 4 are accompanied by the electron transfer between the Sb-N layers and N 2 dimers. Moreover, the nitrogen-rich SbN 4 has a higher energy density of 2.42 kJ g -1 and is a potentially high energy density material.