Hydrogenation of dicyclopentadiene (DCPD) to tetrahydrodicyclopentadiene (THDCPD) over nickel alloy catalyst SRNA-4 has been studied. GC–MS analysis showed that the reaction is a consecutive process with two hydrogenated intermediates. DFT simulation confirmed the double bond in norbornene ring is easier to saturate than that in cyclopentene ring, so the major intermediate is 8,9-dihydrodicyclopentadiene (8,9-DHDCPD). In comparison with Raney Ni, SRNA-4 shows a significantly higher activity and makes the reaction proceed at lower temperature. The reaction conditions including temperature and hydrogen pressure were optimized. The optimal hydrogen pressure is 1.5 MPa. To avoid the decomposition of DCPD, a two-stage operation was designed: 373 K for 1 h and then 403 K for another 4 h. Under these conditions, the yield of THDCPD reaches 98.5%. The apparent kinetics was also calculated using the concentration–time data obtained in the experiments. The activation energy for DCPD to 8,9-DHDCPD and 8,9-DHDCPD to THDCPD reaction is 22.8 kJ/mol and 40.9 kJ/mol, respectively.