Solvent dynamics in alcohols are measured by examining the time dependent Stokes shift of the emission from the twisted intramolecular charge transfer state of bis(4‐(dimethylamino)phenyl) sulphone (DMAPS). The solvation times deviate from the dielectric continuum prediction of τL, the longitudinal relaxation time of the solvent, but generally fall between τL and the Debye relaxation time, τD. The differences between the observed rates of solvation and those predicted by models based on a dielectric continuum description of the solvent reveal the importance of the underlying molecular aspects of solvation.