We investigated the effect of coupled quantum wells to reduce electron overflow in InGaN/GaN dot-in-a-wire phosphor-free white color light-emitting diodes (white LEDs) and to improve the device performance. The light output power and external quantum efficiency (EQE) of the white LEDs with coupled quantum wells were increased and indicated that the efficiency droop was reduced. The improved output power and EQE of LEDs with the coupled quantum wells were attributed to the significant reduction of electron overflow primarily responsible for efficiency degradation through the near-surface GaN region. Compared to the commonly used AlGaN electron blocking layer between the device active region and p-GaN, the incorporation of a suitable InGaN quantum well between the n-GaN and the active region does not adversely affect the hole injection process. Moreover, the electron transport to the device active region can be further controlled by optimizing the thickness and bandgap energy of this InGaN quantum well. In addition, a blue-emitting InGaN quantum well is incorporated between the quantum dot active region and the p-GaN, wherein electrons escaping from the device active region can recombine with holes and contribute to white-light emission. The resulting device exhibits high internal quantum efficiency of 58.5% with highly stable emission characteristics and virtually no efficiency droop.