Herein, highly dispersed Fe species supported on activated carbon (CA-Fe-C) was fabricated with the aid of citric acid, showing excellent catalytic performance and stability for the degradation of rhodamine B (RhB) through peroxymonosulfate (PMS) activation. The radical quenching study, electron paramagnetic resonance (EPR) measurement and PMS consumption analysis confirmed the RhB degradation mechanism involving reactive radical species attacking RhB and non-radical oxidation pathway. The main degradation intermediates were identified by LC-MS, and the possible RhB degradation pathways were deduced. A multivariate quadratic polynomial model was developed using the response surface methodology (RSM) to examine how the removal of RhB was influenced by several quantifiable factors, with the objective of optimizing RhB removal. The analysis of variance (ANOVA) was used to evaluate the adequacy and significance of the proposed model. The effects of solution pH values, initial concentration, inorganic anions, PMS dosage, catalyst dosage, and metal loading amount on RhB removal were investigated. The method of initial rates was employed to determine the intrinsic reaction rate law, and the reaction was identified to follow the Langmuir-Hinshelwood (L-H) kinetics model.