The polarity-responsive probe 5-(dimethylamino)-1-naphthalenesulfonic acid (DNS) was used to explore changes in dendrimer structure that may occur with pH titration. It was found that the fluorescence quantum yield and Stokes shift of DNA vary with solvent polarity and to a lesser extent with solvent microviscosity. Polar solvents stabilized a twisted intramolecular charger transfer (TICT) species.