A series of novel biphenylyl-substitutcd PPV derivatives, polymers 1-4, with different substitution patterns, has been synthesized and characterized. These polymers possess excellent solubilities, good thermal stabilities, and high-photoluminescent efficiencies. H-1 NMR measurements indicated that the polymers contain negligible tolane-bisbenzyl (TBB) structural defects. Light-emitting diodes fabricated from the four polymers with the configuration of ITO/PEDOT:PSS (50 nm)/polymer (80 nm)/LiF (0.4 nm)/Ca (20 nm)/Ag emitted a saturated green light and demonstrated maximum current efficiencies of 5.1, 4.5, 4.7, and 1.4 cd/A for polymers 1-4, respectively. The much higher current efficiencies of polymers 1-3 than polymer 4 are ascribed to more balanced charge transport in the polymer layers of the three polymers, which has been confirmed by time of flight (TOF) charge mobility measurement. The hole mobilities of the polymers at the applied electric field of 2.0 X 10(5) V/cm are 4.70 X 10(-6), 3.83 X 10(-6), 7.21 X 10(-6), and 1.76 X 10(-5) cm(2)/Vs for polymers 1-4. This research indicated that fine tuning the substitution pattern of the polymer side chains is an effective way to optimize the LED device performance by controlling the structural defects as well as balancing the charge mobility of the polymers. (c) 2006 Elsevier Ltd. All rights reserved.