•PLED devices based on different molecular weights of PVK were produced.•Four PEDOTs of different resistivity and work function were investigated.•High work function and resistivity PEDOT produces the best devices.•SETFOS 3.2 simulations were used to verify the experimental results.The effect of a commonly used hole injection layer, poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT–PSS), on polymer light-emitting diode (PLED) performance has been investigated. A series of four different types of commercial PEDOT–PSS, with varying resistivity and work function were examined in devices with the structure Indium Tin Oxide (ITO)/PEDOT–PSS/High Molecular Weight Poly(n-vinylcarbazole) (PVKH): 30% N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD)/Low molecular Weight Poly(n-vinylcarbazole) (PVKL): 40% 2-(4-Biphenyl)-5-(4-tert-butylphenyl)-1,2,4-oxadiazole (PBD): 8% Ir(ppy)3. It was found that the PEDOT–PSS with the highest work function and resistivity produced the devices with the highest efficiencies; this is due to the improved hole injection effect, the decrease in electron leakage current and the prevention of pixel crosstalk. A maximum device current efficiency of 33.4 cd A−1 has been achieved for the most resistive PEDOT; this corresponded to an external quantum efficiency (E.Q.E.) of 11%. Increasing the work function of the PEDOT used resulted in a 60% increase in E.Q.E. and device efficiency for PEDOTs in the same resistivity range. Drift–diffusion simulations, carried out using SEmiconducting Thin Film Optics Simulation software (SETFOS) 3.2, produced J–V curves in good agreement with the experimentally observed results; this allowed us to extract qualitative values for the effective device mobility along with the PEDOT work function and resistivity.