The complete active space (CAS) SCF method and multiconfigurational second-order perturbation theory (CASPT2) have been used to study the electronic spectra of indole, indene, benzimidazole, and 7-azaindole. The paper is focused on the study of the low-lying valence triplet and singlet electronic states at the optimized geometries of the excited states. The geometries have been optimized by using analytic CASSCF derivatives. CASPT2 point calculations have been performed in order to obtain band origins and relaxed emission energies. The results are analyzed in the context of the complex emission processes, both fluorescence and phosphorescence, displayed by the title compounds, which can be used as biochemical probes in the characterization of protein properties and activity.