AbstractFour novel poly(aryl ether)s (P1–P4) consisting of alternate isolated electron‐transporting (3,3″′‐bis‐trifluoromethyl‐p‐quaterphenyl for P1, P3 or 3,3″′‐dicyano‐p‐quaterphenyl for P2, P4) and hole‐transporting fluorophores [N‐(2‐ethylhexyl)‐3,6‐bis(styryl)carbazole for P1, P2 or 9,9‐dihexyl‐2,7‐bis(styryl)fluorene for P3, P4] were synthesized and characterized. These poly(aryl ether)s can be dissolved in organic solvents and exhibited good thermal stability with 5% weight‐loss temperature above 500 °C in nitrogen atmosphere. The photoluminescent (PL) spectra of the films of these polymers showed maximum peaks at around 442–452 nm. The PL spectral results revealed that the emission of polymers was dominated by the fluorophores with longer emissive wavelength via the energy transfer from p‐quaterphenyl to 3,6‐bis(styryl)carbazole or 2,7‐bis(styryl)fluorene segments. Therefore, the p‐quaterphenyl segments function only as the electron‐transporting/hole‐blocking units in these polymers, and the other segments are the emissive centers and hole‐transporting units. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital energy levels of these polymers were measured by cyclic voltammetry. The electron‐donating nitrogen atom on carbazole resulted in the higher HOMO energy levels of P1 and P2 than those of P3 and P4. The single‐layer light‐emitting diodes (LED) of Al/poly(aryl ether)s (P1–P4)/ITO glass were fabricated. P1, P2, and P4 revealed blue electroluminescence, but P3 emitted yellow light as a result of the excimer emission. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2215–2224, 2002