Owing to their narrow bright emission band, broad size-tunable emission wavelength, superior photostability, and excellent flexible-substrate compatibility, light-emitting diodes based on quantum dots (QDLEDs) are currently under intensive research and development for multiple consumer applications including flatpanel displays and flat lighting. However, their commercialization is still precluded by the slow development to date of efficient QD-LEDs as even the highest reported efficiency of 2.0% cannot favorably compete with their organic counterparts. Here, we report QD-LEDs with a record high efficiency (̃4%), high brightness (̃6580 cd/ m2), low turn-on voltage (̃2.6 V), and significantly improved color purity by simply using deoxyribonucleic acid (DNA) complexed with cetyltrimetylammonium (CTMA) (DNA-CTMA) as a combined hole transporting and electron-blocking layer (HTL/EBL). This, together with controlled thermal decomposition of ligand molecules from the QD shell, represents a novel combined, but simple and very effective, approach toward the development of highly efficient QD-LEDs with a high color purity.