A device structure is used in which the hole-transporting layer (HTL) of an OLED is doped with either fluorescent or phosphorescent emitters, that is, anode/HTL-host/hole blocker/electron-transporting layer/cathode. The HTL hosts have higher HOMO energy allowing holes to be transported without being trapped by dopant molecules, avoiding direct recombination on the dopant. The unconventional mismatch of HOMO energies between host and dopant allow for the study of energy transfer in these host/guest systems and triplet exciton diffusion in the HTL-host layers of OLED devices, without the complication of charge trapping at dopants. The host materials examined here are tetraaryl-p-phenylenediamines. Data shows that Förster energy transfer between these hosts and emissive dopant in devices is inefficient. Triplet exciton diffusion in these host materials is closely related to molecular structure and the degree of intermolecular interaction. Host materials that contain naphthyl groups demonstrate longer triplet exciton diffusion lengths than those with phenyl substituents, consistent with DFT calculations and photophysical measurements.