Two oxo-containing neptunium(IV) tert-butoxides, [Np3O(OtBu)10] (1) and [K4Np2O(OtBu)10] (2), were synthesized using the ligand substitution between neptunium(IV) silylamides and HOtBu, whereas the salt metathesis between [NpCl4(DME)2] (DME = dimethoxyethane) and various amounts of LiOtBu resulted in the formation of oxo-free alkoxides [Np(OtBu)4(py)2] (3; py = pyridine) and [Li(THF)]2[Np(OtBu)6] (4; THF = tetrahydrofuran). These complexes are the first structurally characterized neptunium(IV) alkoxides using single-crystal X-ray diffraction and solid-state absorption spectroscopy, which provide data for the development of anhydrous metal-organic neptunium chemistry.