Novel Langmuir–Schaefer (LS) films composed of all aromatic molecules have been studied as resist materials for use in scanning probe lithography. These materials are ideally suited for electrochemical applications for two reasons: First, the mass transport and electron transfer blocking ability of the films can be easily controlled by the number of layers transferred to the substrate; second, the fidelity of the tip induced features is high due to the mechanical properties of the film. We have used the tungsten tip of a scanning tunneling microscope to define square features with lateral dimensions of 1×1 μm into LS films transferred to Au(111) substrates. The dependence of feature depth and morphology on tunneling conditions was also investigated: Well-defined features can be produced only over a narrow range of tip-to-sample distances. Direct electrodeposition of Cu from aqueous solution has been used to metallize the lithographically defined domains.