Electrophosphorescent devices with ionomer-type hole transport layers were investigated. On top of the 3,4-ethylenedioxy thiophene:poly(4-styrene sulfonate) [PEDOT:PSS] structures, fluoropolymer interfacial layers (FPIs) with different side chain lengths were introduced. Both for the PEDOT:PSS/FPI (layered) and PEDOT:PSS (mixed) structures with soluble phosphorescent emitters, the short-side-chain FPIs showed higher efficiency. The difference in the electrical properties of the two FPIs for bipolar (light-emitting) devices was not clear, but the hole-only device clearly showed the favored hole injection at the PEDOT:PSS/FPI structure with a shorter side chain, a copolymer of tetrafluoroethylene and sulfonyl fluoride vinyl ether.