Conjugated polyimides (PI) are successfully synthesized by chemical imidization through in situ silylation of diamines by the alteration of different donor-acceptor monomers. A detailed photophysical characterization is performed in the monomers and different polymers in tetrahydrofuran solutions. The emission spectra of the related donor-acceptor polymers with electron withdrawing cyano groups showed broader and more intense fluorescence bands in comparison to the polymer without -CN groups. The new emission band results from the contribution of two different charge-transfer (CT) pathways: (i) An intramolecular CT (ICT) state in the donor monomers due to the presence of strong electron withdrawing CN groups, and (ii) a intramolecular CT complex (CTC) in the PI polymer between the donor-acceptor monomers, which is red-shifted and shows longer lifetime respect to the ICT of the diamine monomers. The very wide emission band is a very interesting feature for obtaining white light from UV light.