Reactions between nanoclusters (NCs) have been studied widely in the recent past, but such processes between NCs and metal-oxide nanoparticles (NPs), belonging to two different size ranges, have not been explored earlier. For the first time, we demonstrate the spontaneous reactions between an atomically precise NC, [Au25(PET)18]− (PET = 2-phenylethanethiolate), and polydispersed copper oxide nanoparticles with an average diameter of 50 nm under ambient conditions. These interparticle reactions result in the formation of alloy NCs and copper-doped NC fragments, which assemble to form nanospheres at the end of the reaction. High-resolution electrospray ionization mass spectrometry (ESI MS), transmission electron microscopy (HR-TEM), electron tomography, and X-ray photoelectron spectroscopy (XPS) studies were performed to understand the structures formed. The results from our study show that interparticle reactions can be extended to a range of chemical systems, leading to diverse alloy NCs and self-assembled colloidal superstructures. © 2023 The Royal Society of Chemistry.