We report a series of uranium complexes stabilized by the pentakis-benzyl-derivatized cyclopentadienyl ligand, CpBn5. Treatment of [UCl4] and [UI3(1,4-dioxane)1,5] with 2 equiv of the potassium salt, CpBn5K, yielded the corresponding complexes [(CpBn5)2UIV(Cl)2] (1) and [(CpBn5)2UIII(I)] (4). Subsequently, tetravalent 1 is either methylated to give [(CpBn5)2UIV(Me)2] (2) or reduced to form trivalent [(CpBn5)2UIII(μ-Cl)2K(OEt2)3] (3). Oxidation of 4 with AgI yields [(CpBn5)2UIV(I)2] (5), which was found to generate rarely observed, linear uranium metallocenes [(CpBn5)2UIV(NCMe)5][X]2 (X = PF6– (6), BPh4– (7)) upon abstraction of the iodide ligands with thallium salts in acetonitrile. All complexes were characterized by 1H NMR spectroscopy, CHN elemental analysis, UV–vis–NIR spectroscopy, and SQUID magnetization measurements. The solid-state molecular structures of 1–7 were determined by single-crystal X-ray diffraction analysis. An in-depth computational analysis revealed the peculiar electronic structure of the linearly coordinated title complex 7 and its closely related, parent [(Cp*)2UIV(NCMe3)5]2+ dication.