The influence of coverage on the structure and bonding of thiophene within chemisorbed overlayers on Cu(111) has been investigated. Normal incidence X-ray standing wavefield absorption (NIXSW) and near-edge X-ray absorption fine structure spectroscopy (NEXAFS) were used to determine the adsorption site and orientation of thiophene. In the low coverage phase the thiophene molecule forms a π-bonded species, adopting an atop adsorption site with a Cu−S separation of 2.62 ± 0.03 Å with the ring inclined by 26 ± 5°. On increasing coverage, thiophene undergoes a compressional phase transformation to a more weakly bound sulfur lone-pair-bonded species. In this new phase the thiophene still occupies an atop site but the Cu−S separation has increased by 0.2 Å and the ring is now inclined at 44 ± 6° to the surface.