We report the results of Born-Oppenheimer molecular dynamics (BOMD) simulations on the aqueous solvation of the SmI3 molecule and of the bare Sm3+ cation at room temperature using the cluster microsolvation approach including 37 and 29 water molecules, respectively. The electronic structure calculations were done using the M062X hybrid exchange-correlation functional in conjunction with the 6-31G** basis sets for oxygen and hydrogen. For the iodine and samarium atoms, the Stuttgart-Koln relativistic effective-core potentials were utilized with their associated valence basis sets. When SmI3 is embedded in the microsolvation environment, we find that substitution of the iodine ions by water molecules around Sm(III) cannot be achieved due to an insufficient number of explicit water molecules to fully solvate the four separate metal and halogen ions. Therefore, we studied the solvation dynamics of the bare Sm3+ cation with a 29-water molecule model cluster. Through the Sm-O radial distribution function and the evolution of the Sm-O distances, the present study yields a very tightly bound first rigid Sm(III) solvation shell from 2.3 to 2.9 angstrom whose integration leads to a coordination number of 9 water molecules and a second softer solvation sphere from 3.9 to 5 angstrom with 12 water molecules. No water exchange processes were found. The theoretical EXAFS spectrum is in excellent agreement with the experimental spectrum for Sm(III) in liquid water. The strong differences between the solvation patterns of Sm(III) vs Sm(II) are discussed in detail.