The next step in the maturing field of nanotechnology is to develop ways to introduce unusual architectural changes to simple building blocks. For nanowires, on-wire lithography (OWL) has emerged as a powerful way of synthesizing a segmented structure and subsequently introducing architectural changes through post-chemical treatment. In the OWL protocol presented here, multisegmented nanowires are grown and a support layer is deposited on one side of each nanostructure. After selective chemical etching of sacrificial segments, structures with gaps as small as 2 nm and disks as thin as 20 nm can be created. These nanostructures are highly tailorable and can be used in electrical transport, Raman enhancement and energy conversion. Such nanostructures can be functionalized with many types of adsorbates, enabling the use of OWL-generated structures as bioactive probes for diagnostic assays and molecular transport junctions. The process takes 13-36 h depending on the type of adsorbate used to functionalize the nanostructures.