Materials under high pressure usually exhibit unique chemical and physical properties. Polynitrogen compounds have received widespread attention as potential high energy density materials. This paper uses CALYPSO crystal structure prediction method to study the structures of ScN6 and ScN7 in 0–100 GPa. Theoretical calculations show that ScN6 is thermodynamically stable above 80 GPa, while ScN7 is thermodynamically stable from 30 GPa to 90 GPa. Furthermore, ScN7 is metastable under ambient conditions, demonstrating that it can be quenched to ambient conditions after high pressure synthesis. The P1¯-ScN6 is a three-dimensional extended fold multi-nitrogen network, and the P1¯-ScN7 contains a five-membered ring and a curved N4 molecular unit. Both P1¯-ScN6 and P1¯-ScN7 contain a lot of N–N single bonds and N=N double bonds. The energy densities of P1¯-ScN6 and P1¯-ScN7 are 3.97 kJ g−1 and 3.12 kJ g−1, respectively. The detonation velocity and detonation pressure of the P1¯-ScN6 phase and P1¯-ScN7 phase are also higher than that of TNT. Excellent energy storage properties and detonation performance show that they can be used as potential high-energy materials. These results opened up a new way for the synthesis of nitrogen-rich compounds.