This study primarily focuses on evaluating the effects of solution matrix and pH for the generation of reactive oxygen species (ROSs) in a Z-nZVI-catalyzed sodium percarbonate (SPC) system to degrade 1,1,1-trichloroethane (1,1,1-TCA) in the absence and presence of a reducing agent (RA), i.e. hydroxylamine. Degradation of 1,1,1-TCA was 49.5% and 95% in the absence and presence of RA. Probe tests confirmed the generation of major hydroxyl radicals (OH•) and minor superoxide species (O2–•), and scavenger tests verified the key role of OH• and less of (O2–•) radicals. Degradation of 1,1,1-TCA decreased significantly in the presence of Cl− and HCO3–, while NO3– and SO42– had negligible effects in the absence of RA. Addition of RA significantly enhanced 1,1,1-TCA degradation by generating more OH• and (O2–•) radicals in the presence of anions. Degradation of 1,1,1-TCA increased in the acidic range (1–5), while an inhibitive trend from neutral to basic (7–9) was observed. In contrast, a significant increase in 1,1,1-TCA degradation was observed with the addition of RA at all pH values (1–9). In conclusion, the anions and pH significantly influenced the generation and intensity of ROSs and 1,1,1-TCA was effectively degraded in the Z-nZVI-catalyzed SPC system in the presence of RA.