Rapid freeze–thaw cycle experiments were carried out on concrete specimens with 0.4, 0.5, and 0.6 water–cement (w/c) ratio in 0% (tap water), 1%, and 5% Na2SO4 solutions, respectively, to study the performance of ordinary concrete resistance to sulfate freeze–thaw cycle. The specimens underwent visual inspection, and mass losses and relative dynamic elastic modulus (RDEM) were measured regularly. Scanning electron microscope observation and X-ray diffraction analysis were conducted on partial specimens after the freeze–thaw cycle experiment. Research results show that due to the coupling effects of freeze–thaw cycle and sulfate corrosion, freeze–thaw cycles of concrete in Na2SO4 solution caused more damages than in tap water. Higher Na2SO4 concentration produced severe damages. Concrete with different w/c ratios exhibit different sulfate freeze–thaw cycle resistances, and concrete with lower w/c ratio usually produces stronger resistance. RDEM loss is considered the control index to determine concrete failure. The corrosion products in Na2SO4 solution freeze–thaw cycle are mainly ettringite and gypsum. With the increase in Na2SO4 concentration, ettringite formation gradually decreases and gypsum formation gradually increases.