Biochar can act as an adsorbent for phosphate removal from water sources, which can be highly beneficial in limiting eutrophication and recycling elemental phosphorus (P). However, it is difficult to use a single biochar material to overcome problems such as low adsorption efficiency, difficulty in reuse, and secondary pollution. This study addresses these challenges using a novel core-shell structure γ-Al2O3/Fe3O4 biochar adsorbent (AFBC) with significant P uptake capabilities in terms of its high adsorption capacity (205.7 mg g−1), magnetic properties (saturation magnetization 24.70 emu g−1), and high reuse stability (91.0% removal efficiency after five adsorption-desorption cycles). The highest partition coefficient 1.04 mg g−1 μM−1, was obtained at a concentration of 322.89 μM. Furthermore, AFBC exhibited strong regeneration ability in multiple cycle trials, making it extremely viable for sustainable resource management. P removal mechanisms, i.e., electrostatic attraction and inner-sphere complexation, were explained using Fourier transform infrared (FT-IR) spectra and X-ray photoelectron spectroscopy (XPS) measurements. A surface complexation model was established by considering the formation of monodentate mononuclear and bidentate binuclear surface complexes of P to illustrate the adsorption process. Owing to its high adsorption efficiency, easy separation from water, and environmental friendliness, AFBC is a potential adsorbent for P recovery from polluted waters.