Anodic polarisation of Nb in warm and concentrated aqueous alkali results in sustained electrodissolution. The process is investigated in NaOH by voltammetric, steady-state and impedance techniques. The j–E steady-state curve is characterised by a current peak and a subsequent plateau extending up to the explored positive limit (8 VSCE). Upon addition of tartrate to the electrolyte the dissolution current increases markedly. In some NaOH+Na tartrate electrolytes a dissolution–precipitation mechanism sets in, with formation of a surface layer which causes a gradual current decrease; this layer is identified by XRD and elemental analysis as a mixed Na and Nb oxide hydrate. Larger currents may be sustained in KOH+K tartrate solutions without any precipitation process. Impedance diagrams recorded in the plateau region are analysed on the basis of the equivalent circuit resulting from the surface charge model; the oxide formation ratio and the main model parameters are estimated and their temperature dependence is discussed.