Ternary alloys of nickel‐palladium‐phosphorus and iron‐palladium‐phosphorus containing 15–20 at.% phosphorus were rapidly quenched from the liquid state. The structures of the quenched alloys were investigated by x‐ray diffraction. Broad maxima in the diffraction patterns, indicative of a glass‐like structure, were obtained for 13–73 at.% nickel and 13–44 at.% iron, with palladium and phosphorus adding up to 100%. The interference functions were evaluated from the coherent x‐ray scattering and used to compute the electronic radial distribution functions for these alloys. Average interatomic distances and coordination numbers were obtained from the radial distribution functions. A linear relationship between interatomic distances and composition, similar to Vegard's law in crystalline systems, was shown for these metallic glasses. The structure of the quenched Ni&sngbnd;Pd&sngbnd;P and Fe&sngbnd;Pd&sngbnd;P alloys could be explained in terms of structural units analogous to those existing in the metal‐rich phosphides. A quasi‐crystalline model based on the Pd3P structure, with nickel or iron substituting for palladium, was shown to give a very satisfactory approximation of the amorphous structure of the Ni&sngbnd;Pd&sngbnd;P and Fe&sngbnd;Pd&sngbnd;P alloys. Such a model was also in good agreement with electrical and magnetic properties measured for these metallic glasses.