Large-area molecular junctions offer a promising pathway toward the scalable implementation of molecular electronic devices, where charge transport is strongly governed by molecular structure and supramolecular organization. In this work, two diketopyrrolopyrrole (DPP) derivatives featuring tailored alkyl chain lengths designed to isolate the DPP moiety from the anchor groups, are used to form well-ordered Langmuir–Blodgett (LB) films. By bridging the gap between single-molecule behavior and collective transport in large-area devices, molecular junctions were first characterized using the ‘scanning tunneling microscopy (STM) touch-to-contact’ method. These junctions exhibit higher conductance than conventional single molecule I(s) measurements, attributed to intermolecular charge-transfer processes enabled by the ordered LB assemblies. Consistent with this enhanced conductance, low transition voltages (V_trans) indicate favorable alignment between the metal electrode Fermi level and the frontier molecular orbitals. To assess device-relevant performance, large-area molecular junctions were fabricated using Eutectic Gallium–Indium (EGaIn) alloy as a soft top electrode. These junctions exhibit high yield and reproducibility, confirming the formation of robust and high-quality junctions that mirror the transport behavior observed at the single-molecule scale. Together, these results establish a consistent transport picture across both small- and large-area junctions identifying the DPP moiety as a highly effective molecular wire. This effectiveness stems from the capability of these DPP derivatives to form well-ordered films exhibiting intermolecular charge-transfer processes, which, combined with a favorable energy-level alignment with the electrodes, ultimately results in high device conductance.