Biocompatible and freestanding TiO2 nanotube membranes with improved photocatalytic activity were fabricated through a water-vapour-assisted annealing treatment at relatively low temperatures. Photoluminescence results and structure characterization prove that the obtained TiO2 nanotube membranes not only possess an enhanced anatase crystallinity from water molecule-intermediated dissolution-precipitation reactions, but are also covered with abundant hydroxyl groups which are hardly influenced by external disturbances. The anatase crystallinity, the superficial hydroxyl groups and the nanotubular morphology of the membrane treated with water vapour thus lead to enhancement in photocatalytic activity. This new approach is simple and time-saving, opening up new opportunities in various areas, including tissue-engineering, watersplitting, dye-sensitized solar cells and photocatalysis.