Total synthesis, where desired organic- and/or bio-molecules can be produced from simple precursors at atomic precision and with known step-by-step reactions, has prompted centuries-lasting bloom of organic chemistry since its conceptualization in 1828 (Wöhler synthesis of urea). Such expressive science is also highly desirable in nanoscience, since it represents a decisive step towards atom-by-atom customization of nanomaterials for basic and applied research. Although total synthesis chemistry is less established in nanoscience, recent years have witnessed seminal advances and increasing research efforts devoted into this field. In this talk, I will discuss our recent work on introducing and developing total synthesis routes and mechanisms for atomically precise metal nanoclusters (and AIE-type luminescent metal nanoclusters). Due to their definite molecular formulae and unique molecule-like physicochemical properties (e.g., HOMO-LUMO transition, strong luminescence and stereochemical activity), atomically precise metal nanoclusters can be regarded as “metallic molecules”, holding potential applications in various practical sectors such as biomedicine, energy, catalysis, and many others. More importantly, the molecular-like properties of metal nanoclusters are sensitively dictated by their size and composition, suggesting total synthesis of them as an indispensable basis for reliably realizing their practical applications.