The new poly(arylene vinylene) derivatives, which are composed of biphenylene vinylene phenylene vinylene, biphenylene vinylene m-phenylene vinylene, terphenylene vinylene phenylene vinylene, and terphenylene vinylene m-phenylene vinylene as backbone and bulky fluorene pendants at each vinyl bridge, were designed, synthesized, and characterized. The obtained polymers showed weight-average molecular weights of 11,100-39,800 with polydispersity indexes ranging from 1.5 to 2.1. The resulting polymers were amorphous with high thermal stability and readily soluble in common organic solvents. The obtained polymers showed blue emission (lambda(max) = 456-475 nm) in PL spectra, and polymer 4 containing terphenylene vinylene m-phenylene vinylene showed the most blue shifted blue emission (lambda(max) = 456 nm). The double layer light-emitting diode devices fabricated by using obtained polymers as emitter emitted bright blue light. The device showed turn on voltage around 6.5 V and brightness of 70-250 cd/m(2). (c) 2006 Wiley Periodicals, Inc.