There is a resurgence of interest in the electronic structure of perylene for its applications in molecular devices such as organic photovoltaics and organic light-emitting diodes. In this study, we have obtained the low-lying singlet states of perylene by exactly solving the Parisar-Parr-Pople model Hamiltonian of this system with 20 sites and 20 electrons in the VB basis where dimensionality is ∼5.92 billion. The triplet states of perylene are obtained using a DMRG scheme with symmetry adaptation. The one- and two-photon states are very close in energy ∼3.2 eV while the lowest triplet state is slightly below 1.6 eV indicating that perylene is a good candidate for singlet fission. To explore the tunability of the electronic states, we have studied donor-acceptor substituted perylenes. The two donors and two acceptors are substituted symmetrically at either the four bay sites or four peri sites. In all the bay substitution and one peri substitution at moderate D/A strength, the optical gap is lowered to about 2.8 eV. These molecules can be used as blue emitters. We have also reported bond orders in all the cases, and perylene as well as substituted perylenes can be viewed as two weakly coupled naphthalenes in the singlet states, but in triplets these bonds tend to be comparable to other bonds in strength. The charge densities in substituted perylenes are mostly localized around the substitution sites in the ground state. The positive spin densities in triplets are concentrated around the peri and bay sites with the remaining sites having small spin densities of either sign.