<p>The dissolution behaviors of lime, limestone, and core–shell structured lime, as well as their effects on dephosphorization behavior were studied. The results show that the slow dissolution of lime in converter slag is mainly attributed to the calcium silicate layer at the lime/slag interface. CO₂ generated by CaCO₃ decomposition can destroy the calcium silicate layer, and thus accelerates the dissolution of limestone and core–shell structured lime. However, in the initial stage, a large amount of CO₂ emission generated by limestone decomposition results in the poor contact between molten slag and limestone, and the dissolution rate is slower in the test of limestone than that of lime. For core–shell structured lime, the initial dissolution rate is not affected due to the lime surface, and is accelerated by the appropriate CO₂ emission. Rapid CaO pickup in molten slag by fast dissolution of the lime sample can remarkably accelerate the dephosphorization reaction. Because of the fastest dissolution rate, the core–shell structured lime slagging mode shows the most promising prospects for the efficient dephosphorization.</p>