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The study reports electrochemical synthesis, phase evolution and hydrogen generation efficiency of anatase, anatase-rutile and anatase-rutile-brookite (ARB) TiO₂ nanotubes for the first time. The SEM and TEM micrographs confirm the tubular morphology of the samples. The presence of anatase, rutile and brookite phases in a single nanotube is confirmed from high resolution TEM analysis. The water splitting efficiency of the three systems are studied under one sun illumination. It is observed that the anatase-rutile-brookite TiO₂ nanotubes are highly efficient compared to anatase-rutile or anatase TiO₂ nanotubes. The hydrogen generated by ARB composites, after four hours of one sun illumination, is found to be nearly twice that of anatase TiO₂ nanotubes and 1.6 times that of anatase-rutile TiO₂ nanotubes. The results suggest that the ARB in single nanotube having two junction interfaces, highly facilitate inter …