Understanding the hydration kinetics and interactions of hydration products of cement components with chlorides is crucial for designing durable cement-based materials. The most reactive component of ordinary Portland cement (OPC), tricalcium aluminate (CA), was investigated on its hydration kinetics, chloride binding behaviors and hydrated phase assemblages through multiple ex-situ and in-situ methods. The hydrated phases of CA demonstrated different chloride binding isotherms in NaCl and CaCl solutions at different ages. Chloride ions can suppress the formation of calcium aluminate hydrates (OH-AFm and CAH) while calcium ions were favorable to increase the content of hydrocalumite (Cl-AFm) and regulate its crystal structure. The carbonation process deteriorated the chloride binding capacity of CA pastes through producing more calcium mono/hemi-carboaluminate phases (Mc/Hc) or forming a solid solution between Mc and Cl-AFm. These findings can be used as a guide for corrosion protection design of cement-based materials.