We report on a new, one-step electrochemical oxidation method for the rapid synthesis of mixed phase, polycrystalline TiO2 porous films with oriented rutile within a few minutes. The orientation as well as the surface chemical composition of rutile nanocrystallites can readily be tuned by adjusting the additive concentrations of HCl or HF in the electrolyte during synthesis. All TiO2 films show similar large specific surface area, which is ideal for the application of photocatalysis and photoelectrocatalysis. Compared to the random-oriented TiO2 film, films with an increasing portion of exposed rutile (101) facets were found to be characterized by enhanced photocatalytic oxidation and photoelectrochemical performances. We also observed a synergistic promotion effect of the orientation and surface F impurity. Most interesting, our tailor-oriented porous TiO2 films prepared using HF as additive show an impressive photocurrent generation at zero bias, which is similar to 50 times higher compared to that of the random-oriented TiO2 film.