Developments in DNA nanotechnology offer control of the self-assembly of materials into discrete nanostructures. Within this paradigm, pre-assembled DNA origami with hundreds of DNA strands allows for precise and programmable spatial positioning of functionalised nanoparticles. We propose an alternative approach to construct multiple, structurally different, nanoparticle assemblies from just a few complementary nanoparticle-functionalised DNA strands. The approach exploits local minima in the potential energy landscape of hybridised nanoparticle-DNA structures by employing kinetic control of the assembly. Using a four-strand DNA template, we synthesise five different 3D gold nanoparticle (plasmonic) tetrameric isomers, akin to molecular structural isomers. The number of different structures formed using this approach for a set of DNA strands represents a combinatorial library, which we summarise in a hybridisation pathway tree and use to achieve deposition of tetrahedral assemblies onto substrates in high yield. The ability to program nanoparticle self-assembly pathways gives unprecedented access to unique plasmonic nanostructures.