Copper-based nanocatalysts have seen great interest for use in synthetic applications since the early 20th century, as evidenced by the exponential number of contributions reported (since 2000, more than 48 000 works published out of about 81 300 since 1900; results from SciFinder using "copper nanocatalysts in organic synthesis" as keywords). These huge efforts are mainly based on two key aspects: (i) copper is an Earth-abundant metal with low toxicity, leading to inexpensive and eco-friendly catalytic materials; and (ii) copper can stabilize different oxidation states (0 to +3) for molecular and nanoparticle-based systems, which promotes different types of metal-reagent interactions. This chemical versatility allows different pathways, involving radical or ionic copper-based intermediates. Thus, copper-based nanoparticles have become convenient catalysts, in particular for couplings (both homo- and hetero-couplings), transformations that are involved in a remarkable number of processes affording organic compounds, which find interest in different fields (medicinal chemistry, natural products, drugs, materials, etc.). Clearly, this richness in reactivity makes understanding the mechanisms more complex. The present review focuses on the analysis of reported contributions using monometallic copper-based nanoparticles as catalytic precursors applied in coupling reactions, paying attention to those shedding light on the reaction mechanism.