Three main-chain aromatic polyethers with different electroactive heterocyclic moieties, 1,4-quinoxaline, 1,3,4-oxadiazole and 1,3,5-triazine, have been synthesized. The polymers are amorphous with glass transition temperatures above 200 8C. The polymers with these high electron affinity units were used as hole blocking/electron transport layers (HBETL) in lightemitting diodes (LEDs) having the HBETL casted on top of a hole transport/emitting PPV layer. In order to compare the influence of the different polyethers on the LED characteristics, three multilayer devices (ITO/PPV/HBETL/Al) with different HBETLs were investigated. Relative to the single layer PPV device, quantum efficiencies were improved by two orders of magnitude in all multilayer devices and power efficiency was increased using poly(quinoxaline ether) as HBETL. To investigate the electrochemical behavior of the three HBETLs, cyclic voltammetry measurements were carried out and the HOMO/LUMO energy values determined from redox potentials were used to understand the hole blocking property. Lowering the onset voltage using the poly(quinoxaline ether) as HBETL in two-layer devices is compatible with the high electron affinity of this polymer.