Self-assembled monolayers (SAMs) formed from bis(4′-methylbiphenyl-4- yl) ditelluride (BBPDTe) precursors on Au(111) and Ag(111) substrates were characterized by high-resolution X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy. BBPDTe was found to adsorb dissociatively on both substrates, resulting in the formation of well-defined, densely packed, and ordered BPTe SAMs, with a larger molecular inclination, a lower packing density, and inferior crystallinity on Au than on Ag. However, both BPTe/Au and BPTe/Ag were not stable under ambient conditions but underwent rapid autoxidation, which affected exclusively the tellurolate headgroups. The BPTe molecules in the oxidized films remained, however, bound to the substrate by the terminal O atoms coordinated to the Te moieties, and the quality of the films, given by parameters such as packing density, degree of orientational order, and average tilt angle of the SAM constituents, was not noticeably affected by the autoxidation. In addition, the BPTe SAMs were compared with the analogous thiol- and selenol-based systems, and common tendencies for the different chalcogen headgroups, ranging from Te to O, were derived.