Fe-based metal organic frameworks (MOFs) as catalysts exhibited great potential in peroxymonosulfate (PMS) activation for organic pollutant decontamination. In this work, a Fe-based MOF S-BUC-21(Fe) with superior catalytic activity in PMS activation to remove atrazine (ATZ) is reported, in which ATZ was completely degraded within 20.0 min in the presence of 0.1 g/L S-BUC-21(Fe), 0.4 mM PMS and LED UV light irradiation. Both the active species capturing experiments and electron spin resonance (ESR) revealed that reactive species like SO4•-, •OH, •O2–, and 1O2 could be generated continuously via ≡Fe2+/≡Fe3+ cycle along with direct or indirect photo-induced electron transfer. According to the reactive oxygen species (ROSs) contribution calculation, SO4•- and 1O2 were found to play major roles in the ATZ degradation process. Furthermore, quantification and the generation pathways of 1O2 were revealed. After 5-runs experiments, S-BUC-21(Fe) exhibited outstanding stability and reusability, maintaining the morphology and structure of used S-BUC-21(Fe) along with 100.0 % ATZ degradation efficiency.