The dual fluorescence spectra of Various model compounds of DMABN varying in acceptor strength are reported. Dual fluorescence occurs irrespective of whether the more allowed L-1(a)-type state is situated above or below the L-1(b)-type state. Chemical bridging of the dimethylamino group makes the charge-transfer (CT) fluorescence band disappear in both cases. Pyramidalization effects are investigated using quantum-chemical modelling. The ionization potential of the dimethyl-amino donor group strongly increases with pyramidalization although the observed CT fluorescence is little affected. It is concluded that both twisting and 'anti-pyramidalization' (rehybridization to sp(2)) are important to explain the emission properties of the CT state.