Certain metastable metallic crystals spontaneously vitrify upon low‐temperature annealing, as recently demonstrated for the high‐temperature solid solution of Cr and Ti. The driving force for the vitrification process can be accounted for by the concomitant decrease in lattice strain energy. Predictions for a number of binary phases are made and compared with preliminary experimental results. Spontaneous vitrification is found in the systems Co‐Nb, Cr‐Ti, Cu‐Ti, Fe‐Ti, Mn‐Ti, and Nb‐Ni.