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A novel silver@silver chloride/carbon nanofiber (Ag@AgCl/CNF) hybrid was synthesized by electrospinning, heat treament, and subsequent in-situ chemical oxidation strategy. The synthesized materials were characterized using XRD, FTIR, UV-Vis DRS, SEM, and EDX. The experimental results reveal that the electrospun AgNO3/PAN was carbonized and reduced to Ag/CNF, the Ag/CNF was then partly oxidized to form Ag@AgCl/CNF in which Ag@AgCl nanoparticles (ca. 10-20 nm in diameter) were uniformly bounded to CNFs (ca. 165 nm in diameter). The obtained Ag@AgCl/CNF was employed for Na2S2O8 activation under visible light irradiation to treat rhodamine B (RhB). A remarkable RhB removal of ca. 94.68% was achieved under optimal conditions, and the influence of various parameters on removal efficiency was studied. Quenching experiments revealed that HO•, SO4•−, 1O2, and O2•− were major reactive oxygen species, in which O2•− played a pivotal role in RhB degradation. A possible mechanistic route for RhB degradation was proposed.