Idioblastic, mm-scale brookite is reported from SiO2-Ba-Fe-rich metasomatic rocks from the carbonatitic Gross Brukkaros Volcanic Field, Southern Namibia. Electron probe microanalysis shows significant concentrations of Nb (12317 wt.% Nb2O5), coupled with Fe, substituting for Ti in the structure. Calculation of the analytical data indicates evolving Fe2+/(Fe2++Fe3+) ratios during crystallization and two distinct substitution mechanisms in operation: 2Ti4+ ⇌ Nb5+ + Fe3+ and 3Ti4+ ⇌ 2Nb5+ + Fe2+. The compositional patterns observed are explained in terms of initial growth in an environment which evolved from oxidizing to reducing. The outermost 10 μm rims of the crystals are characterized by oxidizing conditions, resulting from a subsequent metasomatic overprint.