This study investigates the photoelectrochemical behavior of STS304 steel with TiO2 thin films coating, applied by sol-gel mehod, for the purpose of cathodic photoprotection of the steel corrosion. One time TiO2-coated STS304 steel, adapted with two kinds of TiO2 sol solution, has the most dominant photopotential abilities, which was -200mV vs. SCE and -500mV vs. SCE under illumination with 40 W fluorescent lamp, respectively. That had yielded more negative values than the corrosion potential of the bare metal(-130mv vs.SCE). The bleaching of TCE was confirmed on TiO2-coated STS304 steel under UV-illumination with 20W Black-light. This Study concluded that Ti02-coated STS304 exhibited both a cathodic photoprotection effect against corrosion and a photocatalytic self-cleaning effect.