In the formation of ZrO2 (zirconia) nanotubes (ZNTs) by anodisation of zirconium, a balance between chemical etching at the surface of the nanotubes and inward growth inside the nanotubes is required. This can be achieved by using fluorinated organic electrolyte like ethylene glycol with the addition of small volume of oxidant. In this work, carbonate was selected as the oxidant and NH4F as the source of fluoride for chemical etching process. Two sets of electrolytes were studied EG/fluoride/Na2CO3 and EG/fluoride/K2CO3. It appears that in the presence of carbonate evolution of gas at the anode during the anodisation process was rather severe. The gas which is likely to be CO2 was found to weaken the adherence between the oxide film with the underlying Zr foil. This induced the formation of free standing ZNTs. High Resolution Transmission Electron Microscope (HRTEM) was used to investigate the crystallinity of the nanotubes where the majority crystal phase of ZNTs was tetragonal/cubic. The ZNTs were used as photocatalysts to oxidize methyl orange dye.