The　elevation　of　environmental　phosphate　levels　can　negatively　impact　both　the　natural　environment　and　human　health.　To　address　this　issue,　a　series　of　MnO2　sorbents　were　investigated　in　this　study.　A　facile　one-pot　synthesis　method　was　employed　to　fabricate　distinct　morphologies　and　crystalline　structures　by　controlling　the　hydrothermal　duration.　As　the　hydrothermal　duration　was　prolonged,　the　samples　demonstrated　a　pronounced　enhancement　of　stability　and　crystalline　phases,　along　with　a　corresponding　increase　in　structural　oxygen　vacancies.　A　series　of　sorption　performance　tests　were　conducted,　including　pH　effect,　sorption　isotherm,　sorption　kinetics,　co-existing　ions　and　sorption–desorption　cycles　experiments.　It　was　revealed　that　manganese　dissolution,　the　surface　charge　of　the　sorbents,　and　the　phosphate　species　at　different　pH　values　collectively　influenced　the　sorption　process.　The　sorbent　α-MnO2-120　h,　with　the　highest　oxygen　vacancy　ratio,　exhibited　the　best　sorption　performance　towards　phosphate　ions,　with　the　maximum　sorption　capacity　at　pH　7.　The　highest　removal　rate　and　kd　value　were　82.63　%　and　2.29　×　103　mL　g−1,　respectively,　at　the　initial　concentration　of　30.7　mg　PO4　g−1.　The　α-MnO2-120　h　sorbent　exhibited　excellent　selectivity　in　the　presence　of　NO3−,　SO42−,　CO32−,　and　SiO32−.　Furthermore,　the　regenerated　material　exhibited　only　a　6　%　decrease　in　phosphate　removal　efficiency　after　five　cycles,　with　no　structural　changes　observed.　A　novel　mechanism　was　proposed,　highlighting　the　dominance　of　covalent　chemical　reactions　in　the　sorption　process.　In　particular,　the　participation　of　oxygen　vacancies　in　sorbents　contributed　to　enhancing　the　effective　removal　of　phosphate　ions.　Overall,　this　study　successfully　demonstrated　that　synthesized　α-MnO2　is　a　promising　sorbent　for　phosphate　removal.　©　2024　The　Author(s)