A clean route is described for the preparation of 1.3% (w/w) supported rhodium nanoparticle (3.0 ± 0.7 nm) catalysts onto commercial ion-exchange resins. Their application to the liquid-phase hydrogenation reaction of CC bonds shows the most active species are obtained under catalytic conditions at room temperature and 1 bar H₂. The heterogeneous catalyst shows excellent activity, selectivity and reusability in the hydrogenation reaction of alkenes and substituted arenes under very undemanding conditions. The results are discussed in terms of support effect on the catalytic efficiency.