A new catalyst system based on rhodium nanoparticles stabilized by polyacrylic acid have been suggested for the hydrogenation of phenols in ionic liquids. It has been shown that high near-quantitative yields of reaction products are achieved in ionic liquids containing a tetraalkylammonium cation. By the TEM and XPS techniques it has been revealed that the use of ionic liquids substantially decreases the particle size and reduces the aggregation of nanoparticles through the inclusion of the ionic liquid cations into the surface layer along with polyacrylic acid.