A comprehensive photophysical. characterization of a new class of naphthalene derivatives of the important alpha -oligothiophenes (alphan's) has been undertaken in solution at room (293 K) and low (77 K) temperature. This includes absorption and fluorescence spectra, fluorescence quantum yields (phi (F)), and lifetimes (tau (F)), as a function of temperature and solvent. Triplet-triplet absorption spectra and triplet formation quantum yields (phi (T)) were also determined. From the above, all the rate constants for the radiative (k(F),) and radiationless (k(IC) and k(ISC)) have been calculated. It is shown that the lowest singlet excited state is an allowed pi,pi* state in all solvents. The results show that although the behavior of the oligomers is similar to their parent compounds (alphan's), significant differences are observed. By comparison of the extinction coefficients of the naph(alphan's) and the (alphan's), a good correlation was found between naph(alphan) and alpha (n + 1). On the basis of this proposed pairing, a consistent blue-shift was observed in the absorption maxima between the compounds here considered and the reference alpha -oligothiophenes. This indicates that there is some significant twist between the naphthalene and the an chromophores. The most favorable inter-ring angle between the two chromophores, naphthalene and alphan, was predicted on the basis of comparison with theory.