A comparative study has been performed on the electronic spectra of a number of unsaturated organic molecules, using on the one hand density functional linear response theory and on the other multiconfigurational second-order perturbation theory, in order to establish the accuracy that the density functional based methods can give for excitation energies and energy surfaces for excited states. The following molecules are included in the study: tetrazine; the five-membered ring systems cyclopentadiene, furan, pyrrole, and thiophene; acetone; and a dipeptide. The results show that DFT valence excited states have errors that vary between 0 and 1 eV, while Rydberg states are accurate to about 0.2eV in most cases. The use of an asymptotically corrected exchange-correlation potential was essential for the latter result. However, transitions which involve a considerable charge transfer have much larger errors. The results show in some cases a surprisingly strong interaction between valence and Rydberg excited states, with considerable effects both on energies and computed intensities.