Self-assembled monolayers (SAMs) of organic molecules provide an important tool to tune the work function of electrodes in plastic electronicsand significantly improve device performance. Also, the energetic alignment of the frontier molecular orbitals in the SAM with the Fermienergy of a metal electrode dominates charge transport in single-molecule devices. On the basis of first-principles calculations on SAMs of
-conjugated molecules on noble metals, we provide a detailed description of the mechanisms that give rise to and intrinsically link theseinterfacial phenomena at the atomic level. The docking chemistry on the metal side of the SAM determines the level alignment, while chemicalmodifications on the far side provide an additional, independent handle to modify the substrate work function; both aspects can be tuned overseveral eV. The comprehensive picture established in this work provides valuable guidelines for controlling charge-carrier injection in organicelectronics and current-voltage characteristics in single-molecule devices.