We report experiments on dendritic molecules with integrated conjugated chromophores that provide microscopic mechanistic information about their solvation dynamics. The fluorescence of a series of immobilized dendritically organized oligothiophenes is studied as they are exposed to good solvents. Initially, the pi-stacking of the oligothiophene units in the dendrimer is destabilized, but full separation of the oligothiophene dendrons takes a time that is orders of magnitude longer due to barriers to torsional motion of the ester linkages. The metastable state prior to separation of the conjugated segments exhibits solution-like spectroscopy but low fluorescence quantum yield relative to the fully solvated segments. This species may play an important role in the photophysics of conjugated oligomer and polymer films. Unusual non-exponential kinetics for the oligothiophene separation step are observed and can be understood in terms of energy transfer among the dendrons.