The first polyoxometalatocyclophanes have been synthesized by the covalent linkage of a hexamolybdate cluster and bisarylimido ligands containing flexible chains. These metallamacrocycles are chiral, and some of them can undergo spontaneous resolution. The work provides a new protocol for preparing chiral polyoxometalates (POMs) and chiral metallamacrocycles from achiral building blocks by fastening both ends of a flexible chain onto an achiral POM to remove the symmetric center and mirror.