Silicate　phase　was　identified　as　the　key　phase　of　smelting　slag　and　also　the　main　constraint　for　its　resource　utilization.　Therefore,　unraveling　the　dissociation　mechanism　of　silicate　phase　was　crucial　for　enhancing　the　resource　utilization　of　smelting　slag.　In　this　study,　the　activation　of　synthesized　pure　olivine　was　utilized　as　a　research　template　to　investigate　the　silicate　phase　activation　mechanism.　The　optimal　conditions　for　olivine　activation　were　established　as　olivine:NaOH:KOH　=　1:5:0.5　(molar　ratio),　roasting　temperature　of　700　°C,　and　roasting　time　of　3　h.　Response　surface　methodology　(RSM)　was　employed　to　verify　the　correlation　of　the　main　influencing　factors　on　the　activation　effect　in　the　order　of　mineral　alkali　molar　ratio　＞　temperature　＞　time.　The　lattice　site　substitution　mechanism　and　the　transformation　law　of　the　physical　phase　of　the　activation　process　were　elucidated　by　DFT　calculations.　The　activation　mechanism　of　silicate　phase　was　revealed　to　involve:　1)　OH-　adsorption　on　cation　sites,　leading　to　the　activation　of　cation-oxygen　bonds　and　the　formation　of　the　hydroxyl　compounds.　2)　K+/Na+　created　a　synergistic　effect　to　fill　the　cation　vacancies,　facilitating　the　gradual　release　of　cations.　This　research　aims　to　offer　theoretical　guidance　for　smelting　slag　treatment　by　providing　a　deeper　understanding　of　the　activation　mechanism　of　silicate-type　minerals.　©　2024　American　Chemical　Society.