The abatement of pharmaceuticals and personal care products (PPCPs), including carbamazepine (CBZ), acetaminophen (ACP) and sulfamethoxazole (SMX), by zero-valent iron (Fe degrees) activated peroxydisulfate (PDS) system (Fe degrees/PDS) in pure water and groundwater was investigated. The removal rates of CBZ, ACP and SMX were 85.4%, 100% and 73.1%, respectively, within 10 min by Fe degrees/PDS in pure water. SO4 center dot-, (OH)-O-center dot and O-2(center dot-) were identified in the Fe degrees/PDS system, and O-2(center dot-) was indicated to play an important role in the ACP degradation. The degradation of PPCPs increased with increasing dosages of Fe degrees and PDS or with decreasing pH and initial PPCP concentrations. Interestingly, the degradation of PPCPs by Fe degrees/PDS was significantly enhanced in groundwater compared with that in pure water, which was partially attributed to SO42- and Cl-. The first-order constants of CBZ, ACP and SMX increased from 0.021, 0.242 and 0.013 mm(-1) to 0.239, 2.536 and 0.259 min(-1), and to 0.172, 1.516 and 0.197 min(-1), respectively, with increasing the concentrations of SO42- and Cl- to 100 mg/L and 10 mg/L, respectively. This study firstly reports the unexpected enhancement of groundwater matrix on the degradation of micropollutants by Fe degrees/PDS, demonstrating that Fe degrees/PDS can be an efficient technology for groundwater remediation.