In the last few years the GaN-based white light-emitting diode (LED) has been remarkable as a commercially available solid-state light source. To increase the luminescence power, we studied GaN LED epitaxial materials. First, a special maskless V-grooved c-plane sapphire was fabricated, a GaN lateral epitaxial overgrowth method on this substrate was developed, and consequently GaN films are obtained with low dislocation densities and an increased light-emitting efficiency (because of the enhanced reflection from the V-grooved plane). Furthermore, anomalous tunneling-assisted carrier transfer in an asymmetrically coupled InGaN/GaN quantum well structure was studied. A new quantum well structure using this effect is designed to enhance the luminescent efficiency of the LED to ∼72%. Finally, a single-chip phosphor-free white LED is fabricated, a stable white light is emitted for currents from 20 to 60 mA, which makes the LED chip suitable for lighting applications.