This paper presents applicability of photocatalytic decomposition of methyl mercaptan using TiO2. A quartz reactor was used in order to elucidate reaction pathway in photocatalytic decomposition of methyl mercaptan. Experimental results showed that more than 99.9% of methyl mercaptan was decomposed within 30 minutes. It was found that the photocatalytic decomposition of methyl mercaptan followed pseudo first order and its reaction coefficient was 0.05min-1 During 30 minutes in the photocatalytic reaction, the concentration of methyl mercaptan, dimethyl disulfide, SO2, H2SO4, COS, H2S were determined. These results showed that 64% of methyl mercaptan were compensated for the increase in sulfur after 30 minutes through the mineralization. The proposed main photocatalytic decomposition pathway of methyl mercaptan was methyl mercaptan→dimethyl disulfide→SO2→H2SO4.