A series of star-like dopant/host single-polymer systems with a D-A type star-shaped orange core and three blue polyfluorene arms were designed and synthesized. Through tuning the doping concentration of the orange core and thermal annealing treatment of white polymer light-emitting diodes based on them, highly efficient white electroluminescence has been achieved. A typical single-layer device (ITO/PEDOT:PSS/polymer/Ca/Al) realized pure white emission with a luminous efficiency of 16.62 cd A-1, an external quantum efficiency of 6.28% and CIE coordinates of (0.33, 0.36) for S-WP-002TPB3 containing 0.02 mol % orange core. The high efficiency of the devices could be mainly attributed to the suppressed concentration quenching of the dopant units, more efficient energy transfer from polymer host to orange dopant and thermal annealing-induced a-phase polyfluorene (PF) self-dopant in amorphous PF host. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012