Fluorescence spectra of water-soluble conducting poly(ethylene oxide)-grafted polydiphenylamines (PDPAg-PEOs with the M(n)s of PEO 350, 750, and 2000) in water were determined and interpreted. The emissions of the PDPA-g-PEOs occurred in the range from 360 to 700 nm and were dependent on their concentrations, PEO chain length, extent of oxidation, pH, and temperature. An optimum concentration, above which the fluorescence intensity decreased dramatically because of quenching, was observed. This quenching was a result of the aggregation of PDPA-g-PEO macromolecules in water. The doped PDPA-g-PEO molecules provided a lower optimum concentration than the corresponding reduced-state macromolecules. A rod-shaped microstructure of nanoscale size was generated through the aggregation of the PDPA-g-PEO macromolecules. This microstructure was also confirmed by dynamic light scattering, atomic force microscopy, and surface elemental analysis.