The absolute photoabsorption cross sections for thiophene in the 5.0-10.7 eV range were measured using synchrotron radiation. New theoretical calculations performed at the time-dependent density functional theory level were used to qualitatively interpret the recorded photoabsorption spectrum. The calculations facilitated a re-analysis of the observed vibronic and Rydberg structures in the photoabsorption spectrum. Here a number of features have been re-assigned, while a number of other features have been assigned for the first time. This represents the most comprehensive and self-consistent assignment of the thiophene high-resolution photoabsorption spectrum to date.