Niobium has been anodized at a constant current density to 10 V with a current decay in 0.8 mol dm(-3) K2HPO4-glycerol electrolyte containing 0.08-0.65 mass% water at 433 K to develop porous anodic oxide films. The film growth rate is markedly increased when the water content is reduced to 0.08 mass%; a 28 mu m-thick porous film is developed in this electrolyte by anodizing for 3.6 ks, while the thickness is 4.6 and 2.6 mu m in the electrolytes containing 0.16 and 0.65 mass% water respectively. For all the electrolytes, the film thickness changes approximately linearly with the charge passed during anodizing, indicating that chemical dissolution of the developing oxide is negligible. SIMS depth profiling analysis was carried for anodic films formed in electrolyte containing similar to 0.4 mass% water with and without enrichment of H-2 O-18. Findings disclose that water in the electrolyte is a predominant source of oxygen in the anodic oxide films. The anodic films formed in the electrolyte containing 0.65 mass% water are practically free from phosphorus species. Reduction in water content increased the incorporation of phosphorus species. (c) 2008 Elsevier Ltd. All rights reserved.