There has been a rejuvenation of interest in the field of metallic glasses in the last decade, ever since the discovery of alloy compositions which allow bulk glass formation. By definition, bulk metallic glasses (BMGs) are characterized by a critical cooling rate < 10 K/s or a minimum dimension > 1mm. We have chosen to examine the structure of the Pd-Ni-P system in order to explain, from an atomic structural point of view, its precipitously high glass-forming ability in this system with respect to those of the binary alloys. With three constituent elements the study of the Pd-Ni-P system remains tractable in comparison to other BMGs that often contain five or more elements. This system has a critical cooling rate lower than 1 K/s and is one of the simplest prototypes of a BMG. However, binary alloys of transition metals (e.g. Pd, Ni, Cu) with metalloids (P, Si, etc.) will not form BMGs even though they can be forced to retain a glassy structure with rapid quenching from the liquid phase.