The title compounds, mu-oxido-bis[(tert-butylselenolato)bis(eta(5)-cyclopentadienyl)niobium(IV)] toluene solvate, [Nb(2)(C(5)H(5))(4)(C(4)H(9)Se)(2)O] x C(7)H(8), and mu-selenido-bis[(tert-butylselenolato)bis(eta(5)-cyclopentadienyl)niobium(IV)], [Nb(2)(C(5)H(5))(4)(C(4)H(9)Se)(2)Se], consist of niobium(IV) centres each bonded to two eta(5)-coordinated cyclopentadienyl groups and one tert-butylselenolate ligand and are the first organometallic niobium selenolates to be structurally characterized. A bridging oxide or selenide completes the niobium coordination spheres of the discrete dinuclear molecules. In the oxide, the O atom lies on an inversion centre, resulting in a linear Nb-O-Nb linkage, whereas the selenide has a bent bridging group [Nb-Se-Nb = 139.76 (2) degrees]. The difference is attributable to strong pi bonding in the oxide case, although the effects on the Nb-C and Nb-Se(t)Bu bond lengths are small.