Lanthanum-based materials are effective for sequestering phosphate in water, however, their removal mechanisms remain unclear, and the effects of environmentally relevant factors have not yet been studied. Hereby, this study explored the mechanisms of phosphate removal using La(OH)3 by employing extended X-ray absorption spectroscopy (EXAFS), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), density functional theory (DFT) and chemical equilibrium modeling. The results showed that surface complexation was the primary mechanism for phosphate removal and in binary phosphate configurations, namely diprotonated bidentate mononuclear (BM-H2) and bidentate binuclear (BB-H2), coexisting on La(OH)3 in acidic conditions. By increasing the pH to 7, BM-H1 and BB-H2 were the two major configurations governing phosphate adsorption on La(OH)3, whereas BB-H1 was the dominant configuration of phosphate adsorption at pH 9. With increasing phosphate loading, the phosphate configuration of on La(OH)3 transforms from binary BM-H1 and BB-H2 to BB-H1. Amorphous Ca3(PO4)2 forms in the presence of Ca, leading to enhanced phosphate removal at alkaline conditions. The contributions of different mechanisms to the overall phosphate removal were successfully simulated by a chemical equilibrium model that was consistent with the spectroscopic results. This study provides new insights into the molecular-level mechanism of phosphate removal by La(OH)3.