Understanding the kinetics and mechanisms involved in early-age hydration of tricalcium aluminate (CA) in chloride solutions holds promise for implementing seawater-mixed concrete in the marine environment, as CA remains the most reactive component of Portland cement (PC), affecting both PC and concrete's early-age hardening and long-term durability. Herein, we conducted a series of meticulously designed ex-situ and in-situ experiments to elucidate the intricate hydration behaviors of CA in various chloride solutions. The results reveal that CA exhibits distinct hydration kinetics and structural evolution processes in different solutions. The rapid precipitation of alumino-ferrite-mono (AFm) and CAH phases contributes to the swift development of hydration heat and storage modulus in water and NaCl solutions, with a slight acceleration observed in the later one. Conversely, the formation of CAH is delayed in CaCl and MgCl solutions before 20 min, with the subsequent precipitation of Cl-AFm enhancing its later production, particularly in CaCl solutions. Ab-initio calculations further elucidate that the acceleration effect of Cl ions originates from the ionization and structurization of hydrated surface Ca ions. However, this positive effect is significantly offset by Cl pairing with counterions, resulting in a dramatic adverse effect of solution Ca ions originated from the negative entropy effect of structuralized water molecules and electrostatic repulsion with like-charged surface Ca ions and solvent dipoles. Our findings provide valuable insights for sustainable and durable designs on cement-based materials mixed with seawater.