Metastable body‐centered‐cubic (bcc) Nb–Cr solid solutions were produced by mechanical alloying over a wide concentration range, and investigated by x‐ray diffraction, differential thermal analysis, and transmission electron microscopy. For comparison, metastable bcc and amorphous Nb–Cr alloys were fabricated by sputtering. Upon annealing, the solid solutions prepared by mechanical alloying undergo a transformation to an amorphous phase. The vitrification is polymorphous for a composition Nb45Cr55whereas two‐phase mixtures of amorphous and bcc phases are formed for other concentrations, indicating that metastable equilibria between these two phases develop upon heat treatment. These results, combined with a detailed analysis of the thermodynamic functions of the system, reveal that the amorphous phase has a lower enthalpy and entropy than the bcc phase near equiatomic composition. In consequence, the Gibbs‐energy curves of bcc and liquid/amorphous Nb45Cr55phases versus temperature exhibit two points of intersection, i.e., two melting points, with the amorphous phase being thermodynamically more stable than the bcc phase at low temperatures. Inverse melting is thus thermodynamically possible in the Nb–Cr system, so that the metastable crystalline phase would melt upon cooling. ©1996 American Institute of Physics.