Developing high-performance catalytic systems for eliminating contaminants effectively in water has received a lot of attention. However, the complexity of practical wastewater poses a challenge for degrading organic pollutants. Non-radical active species with strong resistance to interference have shown great advantages in degrading organic pollutants under complex aqueous conditions. Herein, a novel system was constructed by Fe(dpa)Cl2 (FeL, dpa = N, N'-(4-nitro-1,2-phenylene) dipicolinamide) activating peroxymonosulfate (PMS). The mechanism study verified that the FeL/PMS system had high efficiency in producing high-valent iron-oxo and singlet oxygen (1O2) to degrade various organic pollutants. In addition, the chemical bonding between PMS and FeL was elucidated by the density functional theory (DFT) calculations. The FeL/PMS system could remove 96% Reactive Red 195 (RR195) in 2 min, which was much higher than other systems involved in this study. More attractively, the FeL/PMS system demonstrated general resistance to interference from common anions (Cl-, HCO3-, NO3- and SO42-), humic acid (HA) and pH changes and were thus compatible with various natural waters. This work provides a new approach for producing non-radical active species, which is a promising catalytic system for water treatment.