Hierarchically macroporous–mesoporous SBA-15 phosphate adsorbent was synthesized via a dual-templating approach, followed by diamino-functionalization and Fe(III) impregnation. The resulting Fe(III)-coordinated diamino-functionalized macroporous–mesoporous adsorbent possessed well-defined and interconnecting macroporous and mesoporous networks. Its maximum adsorption was 12.7mg/g, which was 86.8% greater than that of Fe(III)-coordinated amino-functionalized mesoporous SBA-15. In the kinetic study of macroporous–mesoporous adsorbent, 92.5% of the final adsorption capacity reached in the first 1min; and the adsorption followed the pseudo-second-order equation well, suggesting the presence of chemisorption. The pH ranging from 3.0 to 6.0 favored the high phosphate adsorption of hierarchically porous adsorbent; however, the coexistence of other anions, especially F − , retarded the adsorption.