The acid–alkaline-inducd corrosive environments inside wastewater concrete pipelines cause concrete structural deterioration and substantial economic losses all over the world. High-performance concrete/mortar (HPC) was designed to have better resistance to corrosive environments, with enhanced service life. However, the durability of HPC in wastewater pipeline environments has rarely been studied. A high-performance mortar mixture (M) reinforced by supplemental materials (including fly ash and silica fume) and polyvinyl alcohol (PVA) fibers, together with a mortar mixture (P) consisting of cement, sand and water with similar mechanical performance, were both designed and exposed to simulated wastewater pipeline environments. The visual appearance, dimensional variation, mass loss, mechanical properties, permeable pore volume, and microstructure of the specimens were measured during the corrosion cycles. More severe deterioration was observed when the alkaline environment was introduced into the corrosion cycles. Test results showed that the M specimens had less permeable pore volume, better dimensional stability, and denser microstructure than the P specimens under acid–alkaline-induced corrosive environments. The mass-loss rates of the M specimens were 66.1–77.2% of the P specimens after 12 corrosion cycles. The compressive strength of the M specimens was 25.5–37.3% higher than the P specimens after 12 cycles under corrosive environments. Hence, the high-performance mortar examined in this study was considered superior to traditional cementitious materials for wastewater pipeline construction and rehabilitation.