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Nanocrystalline TiO(2) films were prepared by magnetron sputtering technique on stainless-steel substrates. The as-deposited TiO(2) thin films were in anatase structure with smooth surface morphology. Decomposition of methyl orange was used to measure the photoelectrocatalytic activity. The degradation rate of methyl orange increased with externally applied potential. To further accelerate the photocatalytic reaction, a novel method was employed by applying an external electric field in the mid-frequency domain. The fastest photocatalytic degradation rate of methyl orange was obtained when the frequency was maintained at 20 kHz with an external anodic bias at 3.0 V.