Substituted oligothiophenes have a long history in the field of organic electronics, as they often combine outstanding electro-optical properties with the ease of synthesis. To assist the rational selection of the most promising structures to be synthesized, there is the demand for tools that allow prediction of the properties of the materials. In this study, we present strategies for synthesis and computational characterization, with respect to the fluorescence behavior of oligothiophene-based materials for organoelectronic applications. In a combined approach, sophisticated computational methodologies are directly compared to experimental results. The M06-2X functional in combination with the polarizable continuum model in a state-specific formulation for excited-state solvation proved to be particularly reliable. In addition, a semiclassical approach for describing the vibrational broadening of the spectra is employed. As a result, a robust procedure for the prediction of the fluorescence spectra of oligothiophene derivatives is presented.