We investigate multiple quantum well [MQW] structures with charge control layers [CCLs] to produce highly efficient blue phosphorescent organic light-emitting diodes [PHOLEDs]. Four types of devices from one to four quantum wells are fabricated following the number of CCLs which are mixed p- and n-type materials, maintaining the thickness of the emitting layer [EML]. Remarkably, such PHOLED with an optimized triplet MQW structure achieves maximum luminous and external quantum efficiency values of 19.95 cd/A and 10.05%, respectively. We attribute this improvement to the efficient triplet exciton confinement effect and the suppression of triplet-triplet annihilation which occurs within each EML. It also shows a reduction in the turn-on voltage from 3.5 V (reference device) to 2.5 V by the bipolar property of the CCLs.