Physical vapor deposition polymerization was achieved by evaporating vinyl monomers followed by heat treatment. This technique was utilized for preparing a hole-transport layer (HTL) and emissive layers (EMLs) of organic light emitting diodes (OLEDs). Adivinyl derivative of tetraphenyidiaminobiphenyl, DvTPD, was used both for the HTL and for the host material of red phosphorescent EML. A vinyl derivative of bis(N-carbazolyl) benzene, vmCP, was used for the host material of blue phosphorescent EML The ELMs were doped with red or blue-emitting phosphorescent iridium complexes modified with styril units. After characterizing the devices that have single EML of red or blue emission, an OLED having multilayered ELM was prepared by stacking these layers to achieve quasi-white emission. It was found that the deposition polymerization was effective to improve the emission efficiency. The improvement appeared to be related to the proper carrier balance in the EML (C) 2009 Elsevier B.V. All rights reserved.