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 center dot) and minor superoxide species (O-2(-center dot)), and scavenger tests verified the key role of OH center dot and less of O-2(-center dot) 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 center dot and O-2(-center dot) 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.