To study the damage evolution behavior of polypropylene fiber reinforced concrete (PFRC) subjected to sulfate attack, a uniaxial compression test was carried out based on acoustic emission (AE). The effect of sulfate attack relative to time and fiber hybridization were analyzed and the compression damage factor was calculated using a mathematical model. The changes to AE ringing counts during the compression could be divided into compaction, elastic, and AE signal hyperactivity stages. In the initial stage of sulfate attack, the concrete micropores and microcracks were compacted gradually under external load and a corrosion products filling effect, and this corresponded with detection of few AE signals and with concrete compression strength enhancement. With increasing sulfate attack time, AE activity decreased. The cumulative AE ringing counts of PFRC at all corrosion ages were much higher than those for plain concrete. PFRC could still produce AE signals after peak load due to drawing effect of polypropylene fiber. After 150 d of sulfate attack, the cumulative AE ringing counts of plain concrete went down by about an order of magnitude, while that for PFRC remained at a high level. The initial damage factor of hybrid PFRC was −0.042 and −0.056 respectively after 150 d of corrosion, indicating that the advantage of hybrid polypropylene fiber was more obvious than plain concrete and single-doped PFRC. Based on a deterioration equation, the corrosion resistance coefficient of hybrid PFRC would be less than 0.75 after 42 drying−wetting sulfate attack cycles, which was 40% longer than that of plain concrete.