The damage process and corrosion ion distribution in concrete, which was exposed to 60 and 170 drying-immersion cycles of sulfate solution, were systematically investigated. The effects of plain concrete, plain concrete mixed with 4 and 8 kg/m3 modified PP fiber and high-performance concrete (HPC) mixed with 0.8 kg/m3 fine PP fiber on the damage process were also studied. The experimental results showed that thenardite-induced surface scaling, as well as gypsum- and ettringite-induced cracks, were the main degradation forms of concrete under attack of sulfate solution and drying–immersion cycles. The relative dynamic modulus of elasticity of concrete initially increased, then reached stability and finally decreased to failure. The sulfate diffusion coefficients of plain and HPC were 10-12 and 10-13 m2/s, respectively. The concentration of sodium ion increased with depth, then maintained stability and finally decreased rapidly with concrete depth. The content of calcium ion on the concrete surface was 110%-150% of that in the interior of specimens. Although fiber worsened the surface scaling of concrete, better resistance capacity of sulfate ion penetration into concrete was observed in plain concrete with 4 kg/m3 modified PP fiber and HPC.