Abstract The valence‐band density of states has been measured for both crystalline Sb and InSb by X‐ray induced photoemission using 1253.6 eV Kα X‐rays of Mg. The results are compared with theoretically determined band structure and density‐of‐states calculations. A peak observed in the InSb curve at −6 eV is interpreted as being due mostly to s—p‐like bands of the Sb.