Absorption and fluorescence spectra of three polymeric azo sulfonamide substances were recorded in various solvents in the range of 300–800nm at room temperature. The solvatochromic behavior of these substances and solvent–solute interactions both specific and non-specific-can be analyzed by means of linear solvation energy relationship concept suggested by Kamlet–Taft. The ground and excited state dipole moments of these substances were also evaluated by solvatochromic shift method. It was observed that the excited state dipole moments (μe) are higher than ground state dipole moments (μg) for all samples. Furthermore polymeric structural configurations show an important role in spectroscopic behaviors of polymeric azo sulfonamide samples.