Chitosan possesses electron-rich amino (-NH2) and hydroxyl (-OH) moieties which can anchor with transition metal ions during synthesis. Herein, chitosan was employed as an additive to prepare bismuth ferrite (BFO) via hydrothermal approach. The characterization studies revealed that adding chitosan during BFO synthesis leads to the creation of more oxygen vacancies. The performance of chitosan modified BFO (CMB) was evaluated as peroxymonosulfate (PMS) activator for ciprofloxacin (CIP) removal. Apparently, the addition of 10 wt% chitosan during BFO synthesis (CMB-10) resulted in 1.7 times increase of performance compared to the pristine BFO. Increasing the catalyst loading and PMS dosage resulted in positive effect with 5.7 and 1.9 times rate enhancement, respectively. The CMB-10 exhibited tolerance against pH variation, water matrix, and interfering species. The scavenging experiments indicated that singlet oxygen (1O2), superoxide radicals (O2•-) and sulfate radicals (SO4•-) played a major role in CIP degradation. These reactive oxygen species were generated from PMS activation via Fe3+/Fe2+ and Bi5+/Bi3+ coupling, and oxygen vacancies on the catalyst surface. The CIP degradation pathways were also elucidated based on the detected CIP intermediates. Overall, this study provides insights into the use of chitosan to prepare sustainable materials for pollutants removal via PMS activation.