The hydrogenation of monocyclic aromatic hydrocarbons by ruthenium catalysts has been investigated in the presence of sulfonated monophosphine ligands with different stereoelectronic properties under biphasic conditions. The effects of (i) the number of sulfonate groups, (ii) the steric demand of the ligand and (iii) the sigma-donor ability of the phosphorus atom have been investigated in the catalytic reactions. The TEM analysis of the catalytically active systems revealed that in situ formed soluble ruthenium nanoparticles (RuNPs) are responsible for the catalytic turnover. The Ru/sulfonated phosphine system with the properly tuned ligand exhibited high activity (8800 h(-1)) and selectivity in the hydrogenation of benzene to cyclohexane. Furthermore, the aqueous phase containing RuNPs could be recycled four times without a considerable loss of activity. [GRAPHICS] .