Four copolymers of 9,9-dihexylfluorene and benzothiadiazole derivatives with or without quinoxaline were newly synthesized via Suzuki coupling reaction and characterized. The conjugated polymers with benzothiadiazole moiety in the main chain emitted green fluorescence, while their reduced polymers showed blue emission due to perturbation in the donor-acceptor structure. The polymers were spin-cast into thin films in the presence or absence of photoacid generator and well-defined fluorescence patterns were fabricated on the films by simple UV irradiation. The polymer was electrospun with poly(methyl methacrylate) to produce flexible fibrous mats. Fluorescence patterning was also conducted onto the electrospun fiber web to obtain a stable and flexible pattern without bending damage.