Challenges in developing adsorbents with sufficient phosphate (P) adsorption capacity, selectivity, and regeneration properties remain to be addressed. Herein, a multi-functionalized high-capacity nanocellulose/alginate hydrogel (La-NCF/SA-PEI [La: lanthanum, NCF: nanocellulose fiber, SA: sodium alginate, PEI: polyethyleneimine]) was prepared through environmentally friendly methods. The La-NCF/SA-PEI hydrogel, featuring a 3D porous structure with interwoven functional groups (amino, quaternary ammonium, and lanthanum), demonstrated a maximum P adsorption capacity of 78.0 mg/g, exceeding most La-based hydrogel adsorbents. The kinetic and isotherm fitting results confirmed the multilayer chemisorption process. Comprehensive experimental results, instrumental analysis, and computational results revealed that the ammonium phosphate complex (NH