The Ca-2(UO2)(CO3)(3) complex has been shown to be the dominant species of uranyl in different aqueous environments, and thermodynamic data of the complexation have been measured accurately recently. However, a detailed understanding of the binding processes with explicit consideration of the water molecules in the presence of common salt ions such as Na+ and Cl- has been lacking. Here we use classical molecular dynamics combined with umbrella sampling to map the complete binding processes and their free-energy profiles leading to formation of the Ca-2(UO2)(CO3)(3) complex from UO22+, CO32-, and Ca2+ in an aqueous NaCl solution to simulate the seawater conditions. We find that the presence of Na+ ions affects the binding between UO22+ and CO32- as well as between [(UO2)(CO3)(3)](4-) and Ca2+ by changing the coordination mode of carbonate to UO22+. The free energies of binding, from our simulations are in good agreement with the experimental data for both pure water and the NaCl solution. Our work shows that free-energy simulations based on classical molecular dynamics simulations can be a useful tool to examine the atomistic process of the ligand binding to form the Ca-2(UO2) (CO3)(3) complex under different aqueous, environments and that the presence of common ions can impact the complexation chemistry of uranyl.