The synthesis and characterization of sterically unencumbered homoleptic organouranium aryl complexes containing U−C σ‐bonds has been of interest to the chemical community for over 70 years. Reported herein are the first structurally characterized, sterically unencumbered homoleptic uranium (IV) aryl‐ate species of the form U(Ar)62− (Ar=Ph, p‐tolyl, p‐Cl‐Ph). Magnetic circular dichroism (MCD) spectroscopy and computational studies provide insight into electronic structure and bonding interactions in the U−C σ‐bond across this series of complexes. Overall, these studies solve a decades‐long challenge in synthetic uranium chemistry, enabling new insight into electronic structure and bonding in organouranium complexes. Uranium unencumbered: The first structurally characterized and sterically unencumbered uranium (IV) homoleptic aryl‐ate species are reported. MCD spectroscopy and computational studies provide insight into electronic structure and bonding interactions across this series of organouranium complexes with exclusively U−C σ‐bonds.