To understand the properties of light-sensitive compounds used in optical limiters having photoinduced charge transfer mechanisms, we have investigated the photophysics of a series of di(2-thienyl-3,4–butyl)polyenes. Spectroscopic measurements were obtained as a function of the number of double bonds(n = 1–8). From analysis of the bandshape of the emission spectra, we found evidence of vibronic coupling between the S1 and S2 excited states. The degree of coupling increased with solvents of high refractive index. The appearance of the cis band in absorption spectra of dithienyl polyenes having 6–8 double bonds suggested equilibria between scis and s-trans conformors. The cis band intensity increased in lower polarity solvents, implying solvent-induced conformation changes in these dyes. Trends in the data reflected the ordering, energy gap between and mixing of 1Bu
* and 1Ag
* excited state configurations.