Atomically precise ligand-protected gold nanoclusters (Au NCs) are a unique class of nanomaterials exhibiting physicochemical properties that can change significantly with only minor modifications to their atomic composition. Consequently, Au NCs show promise as building blocks for functional nanomaterials that can be realized via self-assembly. Herein, the controlled functionalization of the ligand shell of Au NCs is exploited to investigate two different strategies to achieve self-assembled architectures based on ultrasmall thiolate (SR)-protected [Au25(SR)18]0 nanoclusters. The first approach utilizes metalloporphyrins as anchoring molecules for Au NCs with the goal to drive self-assembly through supramolecular interactions. The second strategy employs a dithiolate linker with a photoswitchable functionality leading to the formation of light-responsive Au NC assemblies. Overall, the work in this dissertation makes important steps toward the use of Au NCs in tailor-made and self-assembled molecular electronic devices.