The growing global demand for shrimp has driven the intensification of shrimp aquaculture, leading to significant environmental challenges due to nutrient-rich wastewater and solid waste. This study developed shrimp shell-derived adsorbents (SSs) by pyrolysis and calcium hydroxide (Ca(OH)2) activation to remove phosphate (PO43−) from aqueous solutions. Ca(OH)2 activated adsorbent achieved higher PO43− removal than adsorbent obtained at higher pyrolysis temperature, with adsorption capacities up to 381.24 mg/g of PO43− at 20 °C. The primary mechanism driving PO43− removal was chemical precipitation between Ca and PO43−. SSs were found to release Ca2+ from hydroxylellestadite (HDL), Ca(OH)2, and calcium carbonate (Ca(CO)3). Additionally, ligand exchange of PO43− by Ca(CO)3 and π-π interactions from aromatic rings further enhanced the PO43− adsorption. SEM-EDS showed PO43− dispersed on the SSs surface. XPS revealed that Ca-O bond was shifted to Ca-P bond with a higher binding energy and a new π-π interaction peak appeared at 293.60 eV. FTIR confirmed ligand exchange between PO43− and CO32−, with the 1400 cm−1 band disappearing and a new 870 cm−1 band appearing. The XRD, FTIR, and XPS analyses confirmed the formation of various calcium-phosphate (Ca-P) groups, including calcium apatite (Ca-apatite), monocalcium phosphate (Ca(H2PO4)2), and dicalcium phosphate (CaHPO4), on the saturated SSs. Specifically, all XPS spectra of Ca-O moved to higher binding energy, reflecting Ca-P linkages. This study provides a sustainable alternative for handling shrimp shell waste and suggests a promising approach for PO43− recovery, thereby contributing to a circular system in shrimp aquaculture.