White organic light-emitting devices (WOLEDs) based on a double-emitting layer (EML) structure were fabricated, while phosphorescent blue and yellow emitters were employed. An ultra-thin layer of non-doped green tris(2-phenylpyridine) iridium [Ir(ppy)3], which was considered as delta-doping layer, was inserted between the two EMLs for optimization. Furthermore, effect of adjusting thickness of this thin layer on device performance was studied. The results showed that the optimized WOLED consisting of 1-nm Ir(ppy)3 EML achieved a maximum luminance of 29,100 cd/m2, maximum external quantum efficiency of 7%, maximum current efficiency of 25.3 cd/A and maximum power efficiency of 7.8 lm/W, together with low efficiency roll-off over a wide luminance range. Meanwhile, the white emission with Commission Internationale del’Eclariage (CIE) coordinates of (0.382,0.446) at a driving voltage of 10 V were observed. The performance enhancement is ascribed to improved charge carrier balance through introduction the highly efficient Ir(ppy)3 as the thin delta-doping layer.