Vertically oriented Ta-W-O nanotube array films were fabricated via the anodization of Ta-W alloy foils in HF-containing electrolytes. HF concentration is a key parameter in achieving well-adhered nanotube array structure. X-ray photoelectron spectroscopy (XPS) and diffuse reflectance measurements confirm the staggered band-alignment between Ta2O5 and WO3, which facilitates the separation of charge carriers. The nanotubes made of Ta-W films containing 10% W showed 100-fold improvement in the measured photocurrent compared to pristine Ta2O5 upon their use to split water photoelectrochemically. This enhancement was related to the efficient charge transport and the red shift in absorption spectrum with increase of the W content, which was asserted by ultrafast transient absorption (TA) spectroscopy measurements. The TA measurements showed the elimination of trap states upon annealing Ta-W-O nanotubes and, hence, minimizing the charge carrier trapping, whereas the trap states remain in pristine Ta2O5 nanotubes even after annealing.