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Using high-resolution x-ray standing waves and low-energy electron diffraction, the structure of Te adsorbed on Ge͑001͒ was studied. A coverage-dependent structural rearrangement was observed between Te coverages of 1 and 0.5 monolayer ͑ML͒. At Te coverages near 1 ML, Te was found to adsorb in a bridge site, as expected. However, at Te coverages near 0.5 ML, a structure unanticipated for Group VI/Group IV adsorption was discovered. Te-Ge heterodimers were formed with an average valency of 5, allowing them to satisfy all surface dangling bonds. The results help explain the efficacy of Te as a surfactant in epitaxial growth of Ge/Si͑001͒.