We report on the temperature-dependent transport behaviors of large-area molecular junctions fabricated with poly-(3,4-ethylene-dioxythiophene) stabilized with polystyrene sulphonic acid (PEDOT:PSS) interlayer electrodes and the archetypal benzenethiol molecules. In this study, we investigated
two different benzenethiol molecules: 4-methylbenzenethiol (MBT) and 1,4-benzenedithiol (BDT), which have the identical backbone structure but different top end-groups. The charge transport through the molecular junctions was dominated by distinct interfacial contact properties between the
PEDOT:PSS electrodes and the component molecules. We also observed that the electrical characteristics of the MBT junctions are influenced by the PEDOT grain size, particularly depending on the annealing temperature.