An improved cooling rate has been achieved by liquid quenching on a hot substrate, which facilitates the preparation of amorphous and metastable crystalline states of refractory‐metal‐based alloys. The effectiveness has been proved by the experimental results for Mo‐Zr and Nb‐Si‐Ge alloys. A single amorphous phase was obtained from 40–60 at. % Zr. In the Nb‐Si‐Ge alloy system, amorphous and metastable A15 phases were obtained in a wide composition range. The superconducting properties and thermal stability of these phases have been studied.