To study the effect of multiple-quantum-well (MQW) structure on emission characteristics of white organic light-emitting diodes (WOLEDs), we fabricate trapping-type and blocking-type MQWs by inserting C545T (green dye) and TPBi, respectively, into hole transport NPB layer (ITO/CuPc/NPB/MADN:rubrene/TPBi/LiF/Al). Bright efficient and stable fluorescent white emission was obtained for the OLED with 2 trapping-type MQWs formed with C545T (thickness: 2 nm). The device current and power efficiency were greatly raised 36% (7.55 cd/A, 4.36 lm/w) relative to that of reference device (5.44 cd/A, 3.40 lm/w). Furthermore, the improvement remained even beyond the roll-off effect caused by high current density. However, the blocking-type MQW structure was difficult to optimize due to too intense blocking effect of TPBi layer. The mechanistic differences between trapping- and blocking-type MQW structures were elucidated using hole-only device and SCLC measurements. The experimental results show that trapping-type MQW structure manipulates hole transport effectively to improve charges balance which is essential in enhancing device performance, making it applicable for facile fabrication of efficient OLEDs.