Self-assembled multilayers, composed of alternating layers of alpha,omega-mercaptoalkanoic acids and Cu2+ ions ("molecular rulers"), are used as organic sidewall spacers and etch resists for the fabrication of registered microstructures with precisely tailored nanometer-scale spacings. The method outlined here eases the stringency of the lithographic processing for patterning second-generation features. Additionally, a new method to lift off the self-assembled multilayered films for the generation of the tailored nanogaps is demonstrated. The advantages of these techniques are discussed. (c) 2007 American Vacuum Society.