Herein, structured non-doped white organic light-emitting diodes (WOLEDs) were designed by combining the emission of a blue exciplex and orange-red phosphorescent ultrathin layer. The device efficiency and spectra were modulated successfully by adjusting the thickness of the exciplex layer and ultrathin layer, respectively. Meanwhile, high efficiency with external quantum efficiency (EQE) ranging from 15% to 22%, power efficiency from 33 lm W -1 to 47 lm W -1 and warm white emission with correlated color temperature (CCT) from 1600 K to 2600 K were realized. The energy transfer process and emission mechanism is also discussed, and the results reveal that the efficient charge trapping and recombination contribute to the improvement of device efficiency and reduce the roll-off efficiency.