The reaction between [UO F ] and an excess of Me SiN in acetonitrile solution results in fluoride-azide exchange and the uranium(VI) dioxodiazide adduct [UO (N ) ⋅CH CN] was isolated in quantitative yield. The subsequent reaction of [UO (N ) ⋅CH CN] with 2,2'-bipyridine (bipy) resulted in the formation of the azido-bridged binuclear complex [(bipy) (UO ) (N ) ]. The triazido anion [(bipy)UO (N ) ] was obtained by the reaction of [UO (N ) ⋅CH CN] with stoichiometric amounts of bipy and the ionic azide [PPh ][N ]. The reaction of [UO (N ) ] with two equivalents of the [PPh ][N ] resulted in the formation of the mononuclear tetraazido anion [UO (N ) ] as well as the azido-bridged binuclear anion [(UO ) (N ) ] . The novel uranium oxoazides were characterized by their vibrational spectra and in the case of [(bipy) (UO ) (N ) ]⋅CH CN, [PPh ][(bipy)UO (N ) ], [PPh ] [UO (N ) ], [PPh ] [UO (N ) ]⋅2CH CN, and [PPh ] [(UO ) (N ) ]⋅4CH CN by their X-ray crystal structures.