Polynitrogen ligands and/in ionic liquids (ILs) are described as a pertinent tandem to efficiently stabilize rhodium nanoparticles (NPs) in the size range of 2.0 nm for catalytic applications. Several N-donor ligands based on bipyridine skeleton were used as extra protective agents in [BMI][PF(6)] and compared in the hydrogenation of functionalized aromatic compounds at 80 °C and under 40 bar H(2). The nature of the bipyridine derivative and its influence on the coordination mode on the particle surface were proposed to explain the observed different kinetic properties. The hydrogenation of various oxygen-containing arenes was investigated and original results were described in the reduction of anisole and cresols as model lignin compounds, providing a significant ratio of ketone derivatives. A first explanation based on possible reaction routes is proposed to justify the formed products.