We present a new terthiophene derivative substituted at the thienyl beta positions with a naphthalenediimide functionalization. The UV-vis absorption and emission spectroscopic properties as well as the electrochemical properties have been discussed to describe its electronic structure. The vibrational Raman data are used to inspect the molecular architecture. All of the experimental data are supported by quantum chemical calculations with different approaches. A close comparison with other terthiophenes available in the literature is conducted, always stressing the effect of the relative orientation of the donor and acceptor groups either with long-axis or short-axis polarizations. The electronic structure of the molecule has been understood in terms of the HOMO-LUMO absolute energy values. A considerable reduction of the band gap from the constituting units to the studied molecule is detected, although electronic interaction is not optimal for this configuration. Fluorescence quenching is interpreted by the possibility of intersystem crossing and internal conversion. Finally, Raman spectroscopy gives additional information of the distribution of conjugation along the molecular domain, of subtle conformational effects, and of the intermolecular interaction by means of temperature-dependent Raman data. This study provides guidelines for controlling the electronic structure and for exploring new strategies pursuing improved dyes.