In this work, glass formation under high-energy ball milling was investigated for a (Ti0.33Zr0.33Hf0.33)50(Ni0.33Cu0.33Ag0.33)40Al10 high-order alloy system with equiatomic substitution for early and late transition-metal contents. For comparison, an amorphous alloy ribbon with the same composition was prepared using the melt-spinning method as well. Structural features of the samples were characterized using x-ray diffraction, transmission electron microscopy, and differential scanning calorimetry. Mechanical alloying resulted in a glassy alloy similar to that obtained by melt spinning. However, the glass formation was incomplete, and a small amount of unreacted crystallites smaller than 30 nm in size still remained in the final ball-milled product. Like the melt-spun glass, the ball-milled glassy alloy also exhibited a distinct glass transition and a wide supercooled liquid region of about 80 K. Crystallization of this high-order glassy alloy proceeded through two main stages. After the primary nanocrystallization was completed, the remaining amorphous phase also behaved as a glass, showing a detectable glass transition and a large supercooled liquid region of about 100 K.