Functionalized molecules that organize to self-assembled monolayers (SAMs) are gaining importance in organic electronic devices. They are fully compatible with flexible substrates, are amenable to low-cost processing, and show reliable film-forming behavior. Highly integrated devices, such as sensor arrays or memories, have also been demonstrated. Starting from auxiliary layers, which improve and modify surfaces and interfaces in traditional thin-film devices, the applications of SAMs develop towards molecular scale electronics, including active molecular device layers and multifunctional SAMs, which fulfill several layer functions of a device within one monolayer. Mixed SAMs make new and tunable device features possible, by stoichiometric control of the composition of different SAM-forming molecules.