Fe–N alloys with crystalline structures different from those obtained at atmospheric pressure were produced by solid-state reaction between Fe and amorphous boron nitride under high pressure. Two new paramagnetic Fe–N phases were obtained at temperatures above 800 K under pressures between 2.0 and 4.0 GPa. One is of cubic structure with lattice constant of 6.114 Å, and another is of orthorhombic structure with lattice constants of a = 4 8.443, b = 4 4.749, and c 4 3.993 Å. ε–Fe3Nx with N contents of 18.1 to 21.4 at.%, which could not be obtained at atmospheric pressure, was produced at pressures of 3.0 to 4.0 GPa and temperatures of 690 to 800 K. The mechanism of formation of ε–Fe3Nx under high pressure is discussed.