Ruthenium nanoparticles (RuNPs) were prepared through the hydrogenation of [Ru(COD)(COT)] (COD = 1,5-cyclooctadiene, COT = 1,3,5-cyclooctatriene) in the presence of diphosphites derived from carbohydrates as stabilizing agents, and interestingly, structural modifications of the diphosphite backbone were found to influence nanoparticle size and dispersity, as well as their catalytic activity in arene hydrogenation.