Trends in x‐ray photoelectron (XPS) spectra of chalcogens which relate to their bonding are discussed. Valence band spectra of disordered S are reported along with measurements in the same apparatus of amorphous Se and Te. Each chalcogen’s spectrum has a minimum about 7 eV belowEF, between the largelyp‐derived states nearerEFand thes‐derived states. Thepstates are split into a largely non‐bonding level nearEFand a bonding peak an energy &Dgr;Epbelow it. The splitting &Dgr;Ep(S, 3.5 eV; Se, 2.9 eV; Te, 2.2 eV) grows with decreasing atomic number, Z, and is found to scale with Pauling’s bond energies. Thesstates exhibit an apparent bonding‐antibonding splitting which also grows with decreasing Z and scales with the increasing overlap of thesorbitals. Although thesstates overlap, comparisons with calculated valence levels in the free atom suggest that most of cohesive energy in the chalcogens is gained by the bonding of thepelectrons, with no major contribution from theselectrons.