γ-Valerolactone (GVL) has been proposed as a sustainable liquid, and could be used for the production of hydrocarbons by using both homogeneous and heterogeneous catalytic systems. The selective reduction of levulinic acid (LA) to GVL is a key transformation for biorefinery concepts based on platform molecules. We report a detailed investigation of the conversion of LA to GVL using molecular hydrogen in the presence of a catalyst in situ generated from Ru(acac)₃, and electronically and sterically characterized alkyl-bis(m-sulfonated-phenyl)- and dialkyl-(m-sulfonated-phenyl)phosphine (R_nP(C₆H₄-m-SO₃Na)_3−n (n = 1 or 2; R = Me, Pr, iPr, Bu, Cp) ligands. The hydrogenation experiments were performed in the range of 5–100 bar H₂ at 140 °C using 0.016 mol% catalyst and 5–20 eqv. of ligand. The effects of hydrogen pressure and Ru/ligand ratio on the LA conversion were determined. The nBuP(C₆H₄-m-SO₃Na)₂ (χ = 12.5, θ_Tol = 153°) showed the highest activity achieving turnover numbers up to 6200 with a yield and selectivity higher than 99% in a solvent, chlorine and promoter free reaction mixture. The catalyst was successfully recycled for six consecutive runs without loss of activity. The characterization of sulfonated and non-sulfonated phosphines indicated that the sulfonation had no significant effect on the steric and electronic properties of the ligands.