The syntheses of new fluorene-based pi-conjugated copolymers: namely, poly((5,5"-(3',4'-dihexyl-2,2';5',2"-torthiophene 1',1'-dioxide))-alt-2,7-(9,9-dihexylfluorene)) (PFTORT), poly((5,5""-(3",4"-dihexyl-2,2':5',2':5",2''':5''',2""-quinquethiophene 1",1"-dioxide))-alt-2,7-(9,9-dihexylfluorene)) (PFTTORTT), and poly((5,5-E-alpha-(2-thienyl)methylene)-2-thiopheneacetonitrile)-alt-2,7 -(9.9-dihexylfluorene)) (PFTCNVT), are reported. In the solid state, PFTORT and PFTCNVT present red-orange emission (with a maximum at 610 nm) while PFTTORTT shows a red emission with a maximum at 666 nm. In all cases, electrochemical measurements have revealed p- and n-dopable copolymers. All these copolymers have been successfully tested in simple light-emitting diodes and show promising results for orange- and red-light-emitting devices.