Treatment of ceric ammonium nitrate (CAN) with varying amounts of sodium neopentoxide led to the isolation of crystalline cerium(IV) complexes [Ce-(OCH(2)tBu)(2)(NO3)(2)(HOCH(2)tBu)(2)], [Ce(OCH(2)tBu)(3)(NO3)(NCCH3)](2), [Ce-2(OCH(2)tBu)(2)(NO3)](2), and [Ce-2(OCH(2)tBu)(9)Na-(THF)] featuring Ce-IV/(OR) ratios of 1:2, 1:3, 1:3.5, and 1:4.5, respectively. The complexes are light-sensitive and prone to ligand redistribution as evidenced by multicomponent NMR spectra as well as the formation of [{Ce(OCH(2)tBu)(4)}(2)(THF)] and the mixed-valent complex [Ce-3(OCH(2)tBu)(9)(NO3)(2)]. The CAN protocol also gave access to the isopropoxide derivative [Ce(OiPr)(3)(NO3)(THF)](2). The reaction of [Et4N]2[CeCl6] (CAC, ceric organoammonium chloride) with different equivalents of Na(OCH(2)tBu) was also impaired by ligand reorganization and ate complexation as detected for the tetravalent cerium complex [Ce-2(OCH(2)tBu)(7)Cl-2]-[Et4N]. Protonolysis of [Ce{N(SiHMe2)(2)}(4)] with 4 equiv of HOCH(2)tBu afforded donor-free homoleptic [Ce(OCH(2)tBu)(4)](3) in quantitative yield. All complexes were characterized by NMR, DRIFT, and UV-vis spectroscopy, as well as paramagnetic susceptibility measurements, X-ray structure analysis, and elemental analysis.