Four novel poly(aryl ether)s consisting of alternate isolated hole-transporting carbazole and electron-transporting 1 3,4-oxadiazole segments were synthesized from the nucleophilic displacement reaction of bis(fluoride) monomers with bis(phenol) monomers. These poly(aryl ethers are soluble in common organic solvents and exhibit good thermal stability with 5% weight loss temperature above 400 C under a nitrogen atmosphere. The photoluminescent (PL) spectra and quantum yields of these polymers are dependent on the composition of the two isolated fluorophores. The formation of exciplex in P3 was observed in the film and solution state and resulted in the lower quantum yield. The quantum yields of P4 in solutions can increase from 0.04 of P3 to 0.36, due to the dilute effect, by introducing the inert bisphenol A segments. However, the PL spectra of P4 only showed a little blue shift in the film state. This means the interchain exciplex still dominated the emission of polymeric films. The HOMO and LUMO energy levels of these polymers have been measured from cyclic voltammetry. All the observations directly proved that the oxidation in polymers started at the hole-transporting segments. Both the electron and hole affinities of these polymers could be enhanced simultaneously due to the introduction of isolated hole-transporting carbazole and electron-transporting 1,3,4-oxadiazole segments.