Most common macrocycles such as crown ethers, porphyrins, and macrocyclic polyamines show versatile, excellent functions in a variety of research fields such as coordination chemistry, supramolecular chemistry, analytical chemistry, and material sciences. Thus, the rational design of a new class of readily synthesized macrocyclic metal ligands is a key to the development of a new category of functionalized macrocyclic metal complexes. Herein, we report one-pot, template syntheses of a new class of metallomacrocycles with a 16-membered tetraoxime cyclic skeleton from a dioxime in the presence of a template transition-metal ion such as Fe2+, Ni2+, Cu2+, Co2+, or Ag+. These metal ions can be easily removed from the mononuclear metallomacrocycles, and, for example, the metal-free tetraoxime ligand was obtained in 90% yield when Fe2+ was used as the template. It would appear that this one-pot, metal-template Pd2+ cyclization efficiently proceeds through continual metal-mediated oxime exchange reactions. Interestingly, which does not afford any cyclized products, formed a 1:1 complex with the macrocyclic ligand. The molecular structures of the metal-free ligand, its 1:1 metal complexes with Fe2+, Ni2+, Cu2+, Pd2+, and Ag+, and a dinuclear complex with Ag+ were fully determined by single-crystal X-ray analyses. UV-visible absorption spectra and cyclic voltammetry measurements of these complexes are also reported.