The structure of diaquobis-μ-(dimethylsulfoxo)bis(dimethylsulfoxo)dilithium tetraphenyl- borate, [Li2(Me2SO)4(H2O)2][BPh4]2, has been determined at 293 K. The compound crystallizes in the triclinic P-1 space group (a = 11.429(2) Å, b = 14.068(3) Å, c = 19.215(4) Å, α = 69.31(3)○, β = 88.98(3)○, γ = 89.03(3)○). The lithium is coordinated to the oxygens of an aquo ligand, a terminal dimethylsulfoxo ligand, and two bridging dimethylsulfoxo ligands. The coordination geometry of each lithium is significantly distorted from a tetrahedron by the twisting of the plane containing the lithium ion and the two bridging dimethylsulfoxo oxygens relative to the plane containing the lithium ion and the terminal dimethylsulfoxo and aquo oxygen atoms. Hydrogen bonding between the aquo hydrogens and the phenyls of the tetraphenylborate anion is observed but does not result in a polymeric structure as has been observed in other lithium tetraphenylborate salts because of the 1:1 ratio of aquo ligands and tetraphenylborate anions.