Fluorene-based copolymers are currently attracting considerable interest for use in a wide range of optoelectronic devices. Here, we present the results of a joint quantum-chemical and experimental characterization of the structural, electronic, and optical properties of an alternating fluorene-triphenylamine copolymer. We compare the results from this study with those from similar studies of polyfluorene. Although calculations are performed for the gas phase and experiments are performed on the solid state, the results from the two methodologies are in good agreement: the relevant electronic levels, HOMO and LUMO, of polyfluorene are found to be destabilized by incorporation of triphenylamine units in the conjugated backbone, whereas the optical properties of polyfluorene chains are largely unperturbed by the presence of triphenylamine.