A hyperbranched conjugated polymer functionalized in periphery with NN-dimethylaniline was synthesized and characterized. Solvatochromic shifts in both absorption and fluorescence spectra, the effects of solvent polarities on the fluorescence quantum yield and fluorescence lifetime were investigated to probe the formation of an intramolecular charge transfer (ICT) state. The peak position of the emission band arising from the ICT state is red-shifted, and the fluorescence quantum efficiency of the polymer decreases with increasing polarity of the solvents.