It is a great challenge to develop solution-processed, polymeric hole-injection layers (HILs) that perform better than small molecular layers for realizing high-performance small-molecule organic light-emitting diodes (SM-OLEDs). We have greatly improved the injection efficiency and the current efficiency of SM-OLEDs by introducing conducting polymer compositions composed of polyaniline doped with polystyrene sulfonate and perfluorinated ionomer (PFI) as the HIL. During single spin-coating of conducting polymer compositions, the PFI layer was self-organized at the surface and greatly increased the film work function. It enhanced hole-injection efficiency and current efficiency by introducing a nearly ohmic contact and improving electron blocking. Our results demonstrate that solution-processed polyaniline HILs with tunable work functions are good candidates for reducing process costs and improving OLED performance.