The ligand effects of triphenylphosphine and its derivatives in the synthesis of monoformyltricyclo [5.2.1.02,6]dec-3-ene (MFTD) and diformyltricyclodecane (DFTD) by hydroformylation of dicyclopentadiene (DCPD) were studied. The results showed that the substituents on the ligand have significant influences on the catalytic activity and the selectivity to MFTD. The electron-withdrawing substituent increased catalytic activity, but decreased the selectivity slightly, and the electron-donating substituent decreased catalytic activity. Considering both of catalytic activity and target product selectivity, triphenylphosphine may be the best choice. Comparing with the one-step synthesis, the two-step synthesis could increase the total selectivity of MFTD and DFTD, which could be over 99%. In the two-step synthesis, triphenylphosphine ligand obtained a high DFTD selectivity of up to 60%, however the other two ligands still gave lower DFTD selectivitie.