This review captures the synthesis, assembly, properties, and applications of copper chalcogenide NCs, which have achieved significant research interest in the last decade due to their compositional and structural versatility. The outstanding functional properties of these materials stems from the relationship between their band structure and defect concentration, including charge carrier concentration and electronic conductivity character, which consequently affects their optoelectronic, optical, and plasmonic properties. This, combined with several metastable crystal phases and stoichiometries and the low energy of formation of defects, makes the reproducible synthesis of these materials, with tunable parameters, remarkable. Further to this, the review captures the progress of the hierarchical assembly of these NCs, which bridges the link between their discrete and collective properties. Their ubiquitous application set has cross-cut energy conversion (photovoltaics, photocatalysis, thermoelectrics), energy storage (lithium-ion batteries, hydrogen generation), emissive materials (plasmonics, LEDs, biolabelling), sensors (electrochemical, biochemical), biomedical devices (magnetic resonance imaging, X-ray computer tomography), and medical therapies (photochemothermal therapies, immunotherapy, radiotherapy, and drug delivery). The confluence of advances in the synthesis, assembly, and application of these NCs in the past decade has the potential to significantly impact society, both economically and environmentally.