Electron overcharge causes rapid luminescence quenching in the quantum dot (QD) emission layer in QD light–emitting diodes (QD–LEDs), resulting in low device performance. In this paper we describe the application of different aromatic thiol ligands and their influence on device performance as well as their behavior in combination with an electron blocking material (EBM). The three different ligands, 1–octanethiol (OcSH), thiophenol (TP), and phenylbutan–1–thiol (PBSH), were introduced on to InP/ZnSe/ZnS QDs referred to as QD–OcSH, QD–TP, and QD–PBSH. PBSH is in particular applied as a ligand to improve QD solubility and to enhance the charge transport properties synergistically with EBM probably via π–π interaction. We synthesized poly-[N,N-bis[4-(carbazolyl)phenyl]-4-vinylaniline] (PBCTA) and utilized it as an EBM to alleviate excess electrons in the active layer in QD–LEDs. The comparison of the three QD systems in an inverted device structure without the application of PBCTA as an EBM shows the highest efficiency for QD–PBSH. Moreover, when PBCTA is introduced as an EBM in the active layer in combination with QD–PBSH in a conventional device structure, the current efficiency shows a twofold increase compared to the reference device without EBM. These results strongly confirm the role of PBCTA as an EBM that effectively alleviates excess electrons in the active layer, leading to higher device efficiency.