The first photoemission spectra are reported for the valence bands of two metallic glasses, Ca0.70Al0.30 and Ca0.50Al0.50, containing only normal metals. It is found that the valence bands dramatically change and split into two parts. Significant structure is observed near the Fermi levels as well. Confirmation comes from soft-x-ray spectroscopy data and band-structure calculations for hypothetical crystalline alloys of similar compositions. © 1982 The American Physical Society.