Two copolymers (P1 and P2), bearing 3,4-ethylenedioxythiophene and fluorene moieties, were synthesized via Sonogashira coupling reaction successfully and P2 contains additional tetrathiafulvalene derivatives (TTFs) as pendants. The structures and properties of copolymer P1 and P2 were investigated by Infrared spectra, UV-visible spectra, and fluorescence spectra. Spectra analyses revealed that the fluorescent intensity of P2 was only 2 % compared to that of P1 in solution. The quenched fluorescent intensity of P2 could be recovered after adding defined moles of Fe(ClO4)(3) as an oxidant. The phenomenon was discussed with aid of computational stimulation in Gaussian 03. Herein, it is believed that intramolecular charge transfer occurs between TTF pendants and polymeric backbone in P2. P2 could be treated as a reporting group in fluorescent testing/switching system.