The data on the compositional dependence of glass-forming ability, glass transition, and properties of bulk metallic glasses (BMGs) are important for understanding the nature and glass-forming ability of metallic glasses and for their application. In this paper, we report the formation of rare-earth-based Pr–(Cu,Ni)–Al pseudo-ternary BMGs with a large bulk glass-forming composition range and distinct glass transition. The compositional dependence of glass-forming ability, glass transition, and properties were systematically studied. The contrasting effects of Al and Pr on glass formation and glass transition, unique elastic properties, and phonon softening of the BMGs are discussed from the structural point of view.