The first α-Keggin anion, ammonium phosphomolybdate (), was first reported by Berzelius in 1826. In 1892, Blomstrand proposed the structure of phosphomolybdic acid and other poly-acids as a chain or ring configuration. Alfred Werner, using the coordination compounds ideas of Copaux, attempted to explain the structure of silicotungstic acid. He assumed a central group,  ion, enclosed by four , where R is a unipositive ion. The  are linked to the central group by primary valences. Two more  groups were linked to the central group by secondary valences. This proposal accounted for the characteristics of most poly-acids, but not all.
In 1928, Linus Pauling proposed a structure for α-Keggin anions consisting of a tetrahedral central ion, , caged by twelve  octahedra. In this proposed structure, three of the oxygen on each of the octahedra shared electrons with three neighboring octahedra. As a result, 18 oxygen atoms were used as bridging atoms between the metal atoms. The remaining oxygen atoms bonded to a proton. This structure explained many characteristics that were observed such as basicities of alkali metal salts and the hydrated form of some of the salts. However the structure could not explain the structure of dehydrated acids.
James Fargher Keggin with the use of X-ray diffraction experimentally determined the structure of α-Keggin anions in 1934. The Keggin structure accounts for both the hydrated and dehydrated α-Keggin anions without the need for significant structural change. The Keggin structure is the widely accepted structure for the α-Keggin anions.