The initial dissolution steps of lithium sulfate (Li₂SO₄) in water were investigated by performing anion photoelectron spectroscopy and density functional theory calculations on the Li₂SO₄(H₂O)_n⁻ (n = 0–5) clusters. The plausible structures of these clusters and the corresponding neutral clusters were obtained using LC-ωPBE/6-311++G(d,p) calculations by comparing the experimental and theoretical vertical electron detachment energies. Two types of structures for bare Li₂SO₄^−/0 were found: a turtle-shaped structure and a propeller-shaped structure. For Li₂SO₄(H₂O)_n⁻ cluster anions with n = 1–3, two kinds of isomers derived from the turtle-shaped and propeller-shaped structures of bare Li₂SO₄⁻ were identified. For n = 4–5, these two kinds of isomers present similar structural and energetic features and thus are not distinguishable. For the anionic clusters the water molecules prefer to firstly interact with one Li atom until fully coordinating it. While for the neutral clusters, the water molecules interact with the two Li atoms alternately, therefore, showing a pairwise solvation behavior. The Li–S distance increases smoothly upon addition of water molecules one by one. Addition of five water molecules to Li₂SO₄ cannot induce the dissociation of one Li⁺ ion because the water molecules are shared by two Li⁺ ions.