Photophysical properties of trans-2-[4-(N,N-dimethylaminostyryl)]pyridine, a "push-pull" molecule, have been studied in different pure solvents. trans-2-[4-(N,N-dimethylaminostyryl)]pyridine exhibits fluorescence from a locally excited state in nonpolar solvents. However, in polar solvents, fluorescence occur from an intramolecular charge transfer state with high dipole moment obtained not only through the rapid relaxation of locally excited state upon a single excitation, but also by the excitation of ground intramolecular charge transfer state. The twisting of the donor moiety with respect to the acceptor moiety results in a complete charge transfer giving highly Stokes-shifted fluorescence in polar solvents. The potential energy surfaces along the donor and acceptor twist coordinates for the ground and first two singlet excited states have been evaluated at density functional theory and time dependent density functional theory levels, respectively. Monocation-neutral and dication-monocation equilibria of trans-2-[4-(N,N-dimethylaminostyryl)] pyridine at both ground and excited states have been studied. © 2013 Elsevier Ltd. All rights reserved.