The microstructural development during annealing in the supercooled liquid region of amorphous Pd 4 6 Ni 3 6 P 1 8 , which is supposedly of phase-separating composition, is compared and contrasted with those of Pd 4 8 Ni 3 2 P 2 0 and Pd 4 0 Ni 1 0 Cu 3 0 P 2 0 . High resolution electron microscopy showed that the as-quenched alloys were fully amorphous while atom probe field ion microscopy (APFIM) showed random solute distributions, typical of amorphous materials. Annealing in their respective supercooled liquid regions did not result in the formation of compositionally-modulated microstructures prior to the onset of crystallisation.