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The effect of top slag basicity on quality of steel treated with SiFe and SiCaBa alloy as exothermic agent in chemical heating was studied. These experiments were carried out in MoSi2 laboratory furnace with 0.2kg molten steel for equilibrium test and 2kg molten steel for simulation test respectively. These results showed that the adjusting basicity of top slag with CaO is effective to prevent rephosphorization and resulphurization, and it is possible to dephosphorize and desulphurize and remove the inclusions from molten steel when basicity R of the top slag is adjusted to 2.0-3.10, and SiCaBa alloy is better than SiFe alloy in this relation.