The boundary conditions and scope of catalytically stimulated synthesis of ordered intermetallics from solid metals are elucidated. The method is applied to the preparation of AlPd5. Its crystal structure has been determined by means of x‐ray powder diffractometry. AlPd5 forms a structurally unmatched ordered variant of the cubic close‐packing of spheres. Above 900 K AlPd5 is merged in the fcc boundary solid solution AlxPd1−x by a first order phase transition. The particular arrangement of the minority component Al and the associated structural distortions are analysed with regard to chemical bonding against the background of the enthalpy ‐driven disorder‐order transition.