Effect of metal complex on hydrogenation of o-chloronitrobenzene (o-CNB) over poly-vinylpyrrolidone stabilized ruthenium colloid (PVP-Ru) has been studied in methanol media under 320 K and 4.0 MPa. The addition of Zn(II) complexes of diamines to PVP-Ru catalyst system leads to significant increase in the activity of PVP-Ru, while the selectivity for o-chloroaniline (o-CAN) maintained similar to 100%. Especially, rate enhancement more than 30 times that over neat PVP-Ru has been achieved in the presence of Zn(trien)Cl-2. It was verified that the incorporation of Zn(II) complexes of multi-amines changed the reaction kinetics.