A hydrogenation process of chloronitrobenzene. The hydrogenation process comprises the steps of producing a nanosized boron-containing nickel catalyst, wherein a ratio of the amount of the boron atom to the amount of the nickel atom in the nanosized boron-containing nickel catalyst is of about 0.1-0.9. Then, the nanosized boron-containing nickel catalyst is placed into a reactor with a chloronitrobenzene an alcohol solvent having carbon number less than four per a molecular and a hydrogenation process is performed to hydrogenating the chloronitrobenzene in hydrogen with a reaction pressure of about 5-40 atm and a reaction temperature of about 40-150° C.