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At present, it is still a challenge to prepare multifunctional composite nanomaterials with simple composition and favorable structure. Here, multifunctional Fe₃O₄@nitrogen-doped carbon (N-C) nanocomposites with hollow porous core-shell structure and significant electrochemical, adsorption and sensing performances were successfully synthesized through the hydrothermal method, polymer coating, then thermal annealing process in nitrogen (N₂) and lastly etching in hydrochloric acid (HCl). The morphologies and properties of the as-obtained Fe₃O₄@N-C nanocomposites were markedly affected by the etching time of HCl. When the Fe₃O₄@N-C nanocomposites after etching for 30 min (Fe₃O₄@N-C-3) were applied as the anodes for lithium-ion batteries (LIBs), the invertible capacity could reach 1772 mA h g⁻¹ after 100 cycles at the current density of 0.2 A g⁻¹, which is much better than that of Fe₃O₄@N-C nanocomposites etched, respectively, for 15 min and 45 min (948 mA h g⁻¹ and 1127 mA h g⁻¹). Additionally, the hollow porous Fe₃O₄@N-C-3 nanocomposites also exhibited superior rate capacity (950 mA h g⁻¹ at 0.6 A g⁻¹). The excellent electrochemical properties of Fe₃O₄@N-C nanocomposites are attributed to their distinctive hollow porous core-shell structure and appropriate N-doped carbon coating, which could provide high-efficiency transmission channels for ions/electrons, improve the structural stability and accommodate the volume variation in the repeated Li insertion/extraction procedure. In addition, the Fe₃O₄@N-C nanocomposites etched by HCl for different lengths of time, especially Fe₃O₄@N-C-3 nanocomposites, also show good performance as adsorbents for the removal of the organic dye (methyl orange, MO) and surface-enhanced Raman scattering (SERS) substrates for the determination of a pesticide (thiram). This work provides reference for the design and preparation of multifunctional materials with peculiar pore structure and uncomplicated composition.