PAN/Ag2S nanofibers prepared by combining conventional electrospinning technology and facile gas–solid reaction were used to activate peroxymonosulfate for Rhodamine B (RhB) degradation by photocatalysis using visible light. The material properties were analyzed by UV–Vis–NIR, XRD, SEM, FTIR, EIS, and BET techniques. The results indicated that Ag2S nanoparticles with a size of ≈10–20 nm were homogeneously attached to the nanofiber surface. The PAN/Ag2S can remove 96.98% RhB (5 mg L−1) after 120 min at pH 7. Through the identification of reactive oxygen species (ROSs) and the calculation of band gap and band potentials, the photocatalytic mechanism was proposed. Results from the identification of ROSs demonstrate that the contribution of the ROSs was in the order of h+ > 1O2 ≈ O2•− ≈ SO4•− > HO• in which h+ has an important role in RhB degradation. The as‐prepared PAN/Ag2S nanofibers with high photocatalytic activity, effective working under visible light, high flexibility, and easy recovery from the aqueous phase, have the potential for practical applications in wastewater treatment.