The railway tunnel concrete lining exposed to sulfate-bearing groundwater beyond 40 years in southwest of China was investigated. Field investigation, sulfate ions content and corroded products analysis, macro/microscopic test were carried out. Results show that under the tunnel concrete lining structure and its served environmental conditions, sulfate solutions permeate concrete lining and accumulate on windward-side of concrete lining, resulting in the increase of sulfate ions content on windward-side and the diffusion of sulfate ions from windward-side to waterward-side, which cause the concrete lining of windward-side damaged seriously but the waterward-side of concrete lining is still in perfect condition. It is confirmed that structural characteristic of tunnel and environmental conditions lead to physical attack with the leaching of concrete and sodium sulfate crystallization as well as chemical corrosion with formation of gypsum in high sulfate concentration and formation of thaumasite in proper temperature rather than formation of ettringite. These achievements can provide academic and technical supports for understanding the deterioration mechanism of concrete lining as well as constructing railway tunnel under sulfate attack.