Under both pyrolysis and combustion condition, HCl removal efficiency for medical waste with Ca-based additives was semi-quantitatively studied by means of TG-FTIR. Additionally, the difference of HCl removal efficiency for PVC and medical waste was compared. Experimental results showed that: 1) Thermal degradation of medical waste mainly took place in two steps under both pyrolysis and combustion condition; 2) HCl emitted at both two steps and HCl concentration increased with the increased of Cl ratio in the medical waste; 3) for the same additive, HCl concentration decreased with the increased of additives amount, that is to say, HCl removal efficiency of medical waste increased as the increased of Ca/Cl molar ratio. Fourth, when Ca(OH)₂ was used as additive, HCl removal efficiency for medical waste combustion was a little higher than that for medical waste pyrolysis, but either CaCO₃ or CaO was used as additive, it was just opposite, more specifically, when CaCO₃ was used as additive with Ca/Cl=1.3, HCl removal efficiency was 5.49% under pyrolysis condition, but that was only 4.24% under combustion condition. Fifth, under the same Ca/Cl molar ratio, HCl removal efficiency for PVC was higher than that for medical waste under both pyrolysis and combustion condition, more specifically, when Ca(OH)₂ was used as additive with Ca/Cl=1, HCl removal efficiency was 64.51% for PVC, but that was only 27.66% for medical waste pyrolysis with 4% Cl under pyrolysis condition.