The electronic spectrum of tetrathiafulvalene (TTF) oriented in a polyethylene film is characterized experimentally using synchrotron radiation linear dichroism from the near-UV to the vacuum-UV region to 56,500 cm–1 (177 nm). The non-planar TTF molecule is shown to have electronic transitions of significant intensity polarized along all three molecular symmetry axes. A procedure for processing linear dichroic data to obtain partial absorbance curves representing different polarization directions is exemplified. The overlapping contributions to eight individual spectral features are furthermore interpreted by the aid of time-dependent density functional theory using CAM-B3LYP / 6-311++G(3df,3pd) with geometry optimized at the B3LYP / 6-311++G(3df,3pd) level within the C2v point group. Additional calculations using larger basis sets as well as other long-range corrected functionals (LC-ωPBE and ωB97XD) yielded similar results. The planar conformer with D2h symmetry is also considered and it is discussed that rapid equilibration via this transition state may contribute to the diffuse nature of some features of the electronic spectrum. The TTF molecule is a dynamic and 3-dimensional chromophore, and these characteristics may serve as a basis for understanding the optical properties of the numerous TTF-based materials finding applications in supramolecular chemistry, molecular electronics and beyond.