In this work, we demonstrate that coordination interactions between Fe3+ and cucurbit[7]uril (CB[7]) can be utilised to build up defined nanoscale spacing layers in metallic nanosystems. We begin by characterising the layer-by-layer deposition of CB[7] and FeCl3·6H2O coordination layers through the use of a Quartz-Crystal Microbalance (QCM) and contact angle measurements. We then apply this layered structure to accurately control the spacing, and thus optical properties, of gold nanoparticles in a Nanoparticle-on-Mirror (NPoM) structure, which is demonstrated via normalising plasmon resonance spectroscopy.