Photoluminescence (PL) was observed from micelles of polypyrrole without substituent groups in various solvents. Chloroform and THF showed a typical fluorescence quenching behavior that can be observed when quencher molecules are added to a micellar solution of fluorescent material. The PL intensity baried depending upon the solvent in the order of DMSO > DMF > NMP > ethanol > toluene > THF. From the results that the LUMO energy level of dopant was below that of polypyrrole in CV experiment and the PL intensity of the same solution did not decreased under photo-excitation at 290 nm, we propose another quenching mechanism for this behavior, photo-induced charge transfer mechanism.