We report the synthesis and characterization of the first terminal imido complex of an Fe–S cluster, (IMes)3Fe4S4=NDipp (2; IMes=1,3‐dimesitylimidazol‐2‐ylidene, Dipp=2,6‐diisopropylphenyl), which is generated by oxidative group transfer from DippN3 to the all‐ferrous cluster (IMes)3Fe4S4(PPh3). This two‐electron process is achieved by formal one‐electron oxidation of the imido‐bound Fe site and one‐electron oxidation of two IMes‐bound Fe sites. Structural, spectroscopic, and computational studies establish that the Fe–imido site is best described as a high‐spin Fe3+ center, which is manifested in its long Fe−N(imido) distance of 1.763(2) Å. Cluster 2 abstracts hydrogen atoms from 1,4‐cyclohexadiene to yield the corresponding anilido complex, demonstrating competency for C−H activation.