An attempt has been made at obtaining a catalyst for hydrogenation of ortho-chloronitrobenzene (o-CNB) to ortho-chloroaniline (o-CAN) which would be both selective and active. Ruthenium has been used as the active phase since it is the most selective of all metals investigated in the above reaction. Catalyst precursors, RuCl₃·3H₂O and NH₄VO₃, were introduced onto an unconventional support – MgF₂ and reduced in hydrogen flow at 673K. The catalysts obtained revealed unusually high activity and selectivity in the reaction of hydrogenation of o-CNB to o-CAN, both in the gas- and liquid phase. The structural study of the Ru-V/MgF₂ catalyst has shown that its high activity and selectivity were determined by the strong metal–support interactions and ruthenium–VO_x species electron interactions.