In the late 1910s, Franz Hein started the investigation of "triphenylchromium" by reacting chromium trichloride with a Grignard reagent, phenyl magnesium bromide.

Such a reaction gave a mixture of phenyl chromium and Hein suggested that it contained a Cr(VI) species, "(C6H5)5CrBr", generated via valence disproportionation.

[1] The actual discovery of bis(benzene)chromium was largely contributed by Ernst Otto Fischer and Walter Hafner in the 1950s.

Ernst Otto Fischer postulated that it might be possible to synthesize a neutral chromium(0) complex with two benzene ligands, which has a sandwich structure, similar to that of ferrocene.

In 1954, Walter Hafner, a PhD student of Ernst Otto Fischer at the time, put the idea into practice.

In 1956, Fischer and Weiss reported the crystal structure of bis(benzene)chromium to be centrosymmetric and has a cubic symmetry.

[11] Electrochemical studies of bis(benzene)chromium suggested that the half-wave potential (E1/2) of the +1/0 couple is around -1.10 to -1.25 V versus Fc+/Fc at 298.15K, depending on the experimental conditions.

[17] In contrast to ferrocene, where 𝝅-interactions dominate the metal-ligand bonds, 𝞭-interactions play a significant role in bis(benzene)chromium.

In late 1990s, Samuel and coworkers revealed that bis(benzene)chromium is an efficient organometallic radical scavenger.