New single-polymer electroluminescent systems containing two individual emission species—polyfluorenes as a blue host and 2,1,3-benzothiadiazole derivative units as an orange dopant on the main chain—have been designed and synthesized. The resulting single polymers are found to have highly efficient white electroluminescence with simultaneous blue (λmax = 421 nm/445 nm) and orange emission (λmax = 564 nm) from the corresponding emitting species. The influence of the photoluminescence (PL) efficiencies of both the blue and orange species on the electroluminescence (EL) efficiencies of white polymer light-emitting diodes (PLEDs) based on the single-polymer systems has been investigated. The introduction of the highly efficient 4,7-bis(4-(N-phenyl-N-(4-methylphenyl)amino)phenyl)-2,1,3-benzothiadiazole unit to the main chain of polyfluorene provides significant improvement in EL efficiency. For a single-layer device fabricated in air (indium tin oxide/poly(3,4-ethylenedioxythiophene): poly(styrene sulfonic acid/polymer/Ca/Al), pure-white electroluminescence with Commission Internationale de l'Eclairage (CIE) coordinates of (0.35,0.32), maximum brightness of 12 300 cd m–2, luminance efficiency of 7.30 cd A–1, and power efficiency of 3.34 lm W–1 can be obtained. This device is approximately two times more efficient than that utilizing a single polyfluorene containing 1,8-naphthalimide moieties, and shows remarkable improvement over the corresponding blend systems in terms of efficiency and color stability. Thermal treatment of the single-layer device before cathode deposition leads to the further improvement of the device performance, with CIE coordinates of (0.35,0.34), turn-on voltage of 3.5 V, luminance efficiency of 8.99 cd A–1, power efficiency of 5.75 lm W–1, external quantum efficiency of 3.8 %, and maximum brightness of 12 680 cd m–2. This performance is roughly comparable to that of white organic light-emitting diodes (WOLEDs) with multilayer device structures and complicated fabrication processes.