In this work, we reported a method for a fabrication of bead-on-string structured g-C3N4/CoFe2O4 composite nanofibers by electrospinning coupled with in situ calcination. For the first time, this catalyst effectively removed high concentrations of mixed organic pollutants through the synergistic effects of adsorption and photocatalysis. The composite materials removal efficiency of adsorption and photocatalytic for high concentrations of organic pollutants in wastewater can exceed 90%. Surface potential analysis using in situ Kelvin probe force microscopy demonstrated the electron transfer pathways on the catalyst surface. The formation of the heterojunction was demonstrated through DFT calculations to significantly enhance the efficiency of electron–hole separation. This work provided valuable insights for the development of efficient catalysts for the synergistic adsorption-photocatalytic treatment of environmental pollutants, thus addressing increasingly severe environmental challenges.