As a high-energy density material, polymeric nitrogen has attracted considerable attention, while the exceptionally high synthesis pressure hinders its studies and applications. A significant discovery indicates that the insertion of noble gas elements can effectively reduce the synthesis pressure of polymeric nitrogen compounds. This work utilized the particle swarm optimization algorithm and first-principles calculations to extensively explore the stoichiometry of Xe–N compounds under high pressures. Two phases of XeN14, P6mm and P-62m, have been discovered, which are energetically more stable than the basic mixture of Xe and N2. Evidence of charge transfer between Xe and N was found, verifying that Xe plays a crucial role in forming polymeric nitrogen compounds. These two compounds are kinetically stable at pressures ranging from 50 to 200 GPa and exhibit semiconductor properties. A unique channel-like structure was discovered in the P6mm phase. The energy densities of P6mm and P-62m phases are 7.39 and 7.59 kJ/g, respectively, significantly exceeding those of TNT (Trinitrotoluene) and HMX (Octogen), indicating their potential as high-energy density materials.