We have investigated the atomic structure and chemical bonding present at sulfur exposed GaAs(111)B‐(2×2) surfaces using both scanning tunneling microscopy (STM) and synchrotron radiation core‐level photoemission. Exposure of the (2×2) surface to a molecular beam of sulfur leads to the appearance of a (1×1) low‐energy electron diffraction pattern which becomes increasingly well defined as the sample is annealed. However, at no stage of the annealing process does the surface display an ordered (1×1) ideal termination. Both the photoemission data and STM images show that a large proportion of the As trimer units of the clean (2×2) surface remain after sulfur exposure and annealing to 450 °C with strong evidence of sulfur substituting for As in atomic layers below the surface. The effect of these reactions is to increase the surface band‐bending from that of the clean (2×2) surface. ©1995 American Institute of Physics.