Two new poly(arylene ethynylenes) were synthesized by the reaction of 1,4-diethynyl-2.5-dioctylbenzene either with 4,4'-diiodo-3,3'-dimethyl-1,1'-biphenyl or 2,7-diiodo-9,9-dioctylfluorene via the Sonogashira reaction, and their photoluminescence (PL) and electroluminescence (EL) properties were studied. The new poly(arylene ethynylenes) were poly[(3,3'-dimethyl-1,1'-biphenyl-4,4'-diyl)1,2-ethynediyl-(2,5-dioctyl-1,4-phenylene)-1,2-ethynediyl] (PPEBE) and poly[(9,9-dioctylfluorene-2,7-diyl)-1,2ethynediyl-(2,5-dioctyl-1,4-pheny lene)-1,2-ethynediyl] (PPEFE), both of which were blue-light emitters. PPEBE not only emitted better blue light than PPEFE, but it also performed better in EL than the latter when the light-emitting diode devices were constructed with the configuration indium-tin oxide/poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonic acid) (50 nm)/polymer (80 nm)/Ca:Al. The device constructed with PPEBE exhibited an external quantum efficiency of 0.29 cd/A and a maximum brightness of about 560 cd/m(2), with its EL spectrum showing emitting light maxima at lambda = 445 and 472 nm. The device with PPEFE exhibited an efficiency of 0.10 cd/A and a maximum brightness of about 270 cd/m(2), with its EL spectrum showing an emitting light maximum at lambda = 473 nm. Hole mobility (mu(h)) and electron mobility (mu(e)) of the polymers were determined by the time-of-flight method. Both polymers showed faster mu(h) values. PPEBE revealed a mu(h) of 2.0 X 10(-4) cm(2)/V(.)s at an electric field of 1.9 X 10(5) V/cm and a mu(e) of 7.0 X 10(-5) cm(2)/V(.)s at an electric field of 1.9 X 105 V/cm. In contrast, the mobilities of the both carriers were slower for PPEFE, and its mu(h) (8.0 X 10(-6) cm(2)/V(.)s at an electric field of 1.7 X 10(6) V/cm) was 120 times its mu(e) (6.5 X 10(-8) cm(2)/V(.)s at an electric field of 8.6 X 10(5) V/cm). The much better balance in the carriers' mobilities appeared to be the major reason for the better device performance of PPEBE than PPEFE. Their highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels were also a little different from each other. (c) 2006 Wiley Periodicals, Inc.