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Vertically aligned ZnO nanotubes were prepared by etching ZnO rod arrays in aqueous solution, which were previously developed by chemical bath deposition method. The morphological, structural, photoluminescence, as well as photocatalytic properties of the ZnO nanotubes were examined with respect to the pH values of chemical bath solution. The morphology of the products was found to be sensitive to the pH values and chemical bath temperatures. The nanotubes synthesized at a low pH value (5.82) exhibited a strong UV emission and a weak defect-related visible emission. The highest photocatalytic efficiency was also observed at pH = 5.82. The possible mechanism for the difference of photocatalytic efficiency was discussed.