“…While, owing to the challenge of discovering metal clusters suitable for making cluster‐OPs, little progress has been achieved in the assembly of cluster‐OPs compared to that of MOPs. The common metal clusters observed in reported cluster‐OPs are 3d transition‐metal clusters, such as the {Cu 2 } dimer, {Fe 3 O(SO 4 ) 3 } trimer, or {Ni 4 Cl} tetramer. Interestingly, during the past decade, a handful of polyoxometalates (POMs) have been successfully used as building blocks to yield a series of novel cluster‐OPs, mainly based on polyoxovanadates {V 3 O 12 }, {V 4 O 16 }, {V 5 O 17 }, {WV 5 O 22 }, {V 6 O 6 (OCH 3 ) 9 (SO 4 )}, and {P 4 V 5 O 20 }, polyoxotungstate {Ni 6 PW 9 O 34 }, and polyoxomolybdate {PMo 9 O 31 }.…”