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In this work, magnetic CuFe₂O₄/Ag nanoparticles activated by porous covalent organic frameworks (COF) was fabricated to evaluate the heterogenous reduction of 4-nitrophenol (4-NP). The core-shell CuFe₂O₄/Ag@COF was successfully prepared by polydopamine reduction of silver ions on CuFe₂O₄ nanoparticles, followed by COF layer condensation. By integrating the intrinsic characteristics of the magnetic CuFe₂O₄/Ag core and COF layer, the obtained nanocomposite exhibited features of high specific surface area (464.21 m²g^-1), ordered mesoporous structure, strong environment stability, as well as fast magnetic response. Accordingly, the CuFe₂O₄/Ag@COF catalyst showed good affinity towards 4-NP via π-π stacking interactions and possessed enhanced catalytic activity compared with CuFe₂O₄/Ag and CuFe₂O₄@COF. The pseudo-first-order rate constant of CuFe₂O₄/Ag@COF (0.77 min^-1) is 3 and 5 times higher than CuFe₂O₄/Ag and CuFe₂O₄@COF, respectively. The characteristics of bi-catalytic CuFe₂O₄/Ag and the porous COF shell of CuFe₂O₄/Ag@COF made a contribution to improve the activity of 4-NP reduction. The present work demonstrated a facile strategy to fabricate COF-activated nano-catalysts with enhanced performance in the fields of nitrophenolic wastewater treatment.