Bimetallic catalysis offers a unique approach to diverse bond activation chemistry, complementing the more widely used monometallic catalysis. In this context, bimetallic complexes of 1,8-naphthyridine motifs have been synthesized and studied to mimic the active sites of metalloenzymes and understand their role in C-C bond formation reactions. Specifically, dicopper(I) complexes with naphthyridine ligands are of significant interest due to their distinctive binding mode, which hinges on the interaction of the copper sites with the available molecular orbitals. These naphthyridine-based dicopper(I) complexes have been promising as catalysts for activating terminal alkynes and arenes, enabling several strategic functionalizations, including copper-catalyzed azide-alkyne coupling reactions. This mini-review highlights the reactivity and selectivity of naphthyridine-based dicopper complexes and their importance in metal-metal or metal-ligand cooperativity.