The structural features of the ammoniated (NH3)K3C60 fulleride are studied by synchrotron X-ray powder diffraction as a function of pressure to 6.7 GPa. A superstructure appears at ∼1 GPa as a result of orientational ordering of both the C60 and K + -NH3 units (orthorhombic symmetry, space group F ddd). The pressure evolution of the lattice constants reveals a highly compressible, strongly anisotropic structure. The centre-to-centre interfullerene separations of ∼10.40 Å in the basal plane are comparable to those in the superconducting cubic analogue, RbCs2C60 and evidently sufficiently short to drive the system superconducting, despite its low crystal symmetry.