A chloride-incorporated dodecavanadate, [V12O32(Cl)](5-) (1) has been synthesized from a dicopper macrocyclic complex, [Cu2V8O24](4-) (2). By using hydrogen cyanide with a chloride guest anion, two copper cations are removed and the presence of chloride anion template affords a new bowl-shaped dodecavanadate, 1, with chloride anion at the center. The 1:1 mixture of 1 and [V12O32(CH3CN)](4-) (3) in acetonitrile shows no V-51 NMR signal scrambling at room temperature suggesting the tight binding of the chloride anion inside the anionic bowl molecule. The dissociation of the chloride anion was only observed at higher temperatures.