In this study, efficient solution-processed organic light-emitting diodes (OLEDs) based on a light-emitting layer composed of a blue emissive phosphorescent dendrimer and exciplex host were investigated. Employing poly(styrene sulfonic acid) doped poly(ethylenedioxythiophene):poly(styrenesulfonate) (m-PEDOT:PSS) as the hole injection layer resulted in devices with external quantum efficiencies (EQEs) over 20% for luminances of up to 100 cd m−2. A feature of these devices was a relatively slow electroluminescence turn-on for the initial voltage scan, which was absent when m-PEDOT:PSS was replaced with molybdenum oxide as the hole injection layer. The initial turn-on rate was found to decrease with increasing PSSH content, with the results suggesting that proton migration from (m-)PEDOT:PSS is the cause of the change in the device performance. The overall device performance was found to be scan dependent, with sequential voltage scans leading to a decrease in EQE, which is ascribed at least in part to electromer formation. We also demonstrate solution-processed OLEDs with the same exciplex host and bis[2-(4,6-difluorophenyl)pyridinato-C2,N](picolinato)iridium(III) (FIrpic) as the emitter, that have maximum EQE and power efficiencies of 17.0% and 25.3 lm W−1, respectively