In this paper, we analyze the degree of intramolecular charge transfer in a push-pull pi-conjugated system, 5-(dimethylamino)-5'-nitro-2,2'-bithiophene, from changes in frequencies and relative intensities of its strongest Raman scatterings in a bunch of solvents with different polarities. Density functional theory (DFT) was used as a support of the experimental study. Solvent effects on the molecular and electronic structures and on the vibrational properties were estimated by performing B3LYP/6-31G** calculations within the framework of the polarized continuum model (PCM) developed by Tomasi. Calculations reveal that the molecule is highly polarized in the ground state and behaves as a very efficient photoinduced push-pull system. The polarization of the molecule strongly increases with solvent polarity and determines that the profile of the Raman spectra greatly changes from one solvent to another and in going to the solid. The strongest Raman scattering associated with the nu(sym)(NO2) stretching undergoes a downshift of 48 cm(-1) in passing from CCl4 to the solid. DFT calculations provide a comprehensive interpretation of the evolution of the Raman spectra with solvent polarity.