We use liquid-phase transmission electron microscopy (TEM) to study self-assembly dynamics of charged gold nanoarrows (GNAs), which reveal an unexpected "colloid-atom duality". On one hand, they assemble following the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory for colloids when van der Waals attraction overruns slightly screened electrostatic repulsion. Due to concaveness in shape, GNAs adopt zipper motifs with lateral offset in their assembly matching with our modeling of inter-GNA interaction, which form into unconventional structures resembling degenerate crystals. On the other hand, further screening of electrostatic repulsion leads to merging of clusters assembled from GNAs, reminiscent of the coalescence growth mode in atomic crystals driven by minimization of surface energy, as we measure from the surface fluctuation of clusters. Liquid-phase TEM captures the initial formation of highly curved necks bridging the two clusters. Analysis of the real-time evolution of neck width illustrates the first-time observation of coalescence in colloidal assemblies facilitated by rapid surface diffusion of GNAs. We attribute the duality to the confluence of factors (e.g., nanoscale colloidal interaction, diffusional dynamics) that we access by liquid-phase TEM, taking turns to dominate at different conditions, which is potentially generic to the nanoscale. The atom aspect, in particular, can inspire utilization of atomic crystal synthesis strategies to encode structure and dynamics in nanoscale assembly.