A comparative study of the electronic transitions of fluorene and its hetero-analogues dibenzofuran, carbazole, and dibenzothiophene was performed in a wide energy range. Gas phase, crystal phase, and linear dichroism electronic transmittance spectra were measured with synchrotron radiation. Electronic transitions to excited singlet states were predicted with time-dependent density functional theory, TD-B3LYP/6-31+G(d,p). Based on the experimental and theoretical results, symmetry assignments of electronic transitions in the vacuum and near-UV region are suggested. The correspondence between excited states in these molecules, similarities, and differences between their electronic spectra are discussed.