While anthracene-N,N-dimethylaniline (AnDMA) has been under investigation for many years, only relatively few reports exist about the compound pyrene-N,N-dimethylaniline (PyDMA). By comparing the observed behavior between these compounds, new conclusions can be drawn regarding the processes during and after the electron transfer. The temporal development of the dynamic Stokes shift of the charge-transfer (CT) emission band and the comparison with a rigid reference compound show that in PyDMA the intramolecular rotation of DMA around the single bond to the pyrenyl is of minor importance, in contrast to the case for AnDMA, in which the rotation around the analogous bond (anthryl-DMA) constitutes the rate-determining factor for the dynamic Stokes shift. PyDMA shows an unusually large fluorescence quantum yield from the CT state of almost 100% in many polar and nonpolar solvents. Therefore, the appearance of amplified stimulated emission (ASE) is readily anticipated. The suitability of PYDMA as a CT laser dye is demonstrated; the emission wavelength of the ASE of the CT dye laser can be adjusted with the choice (of the polarity) of the solvent over a wide range.