The oligomerization of α-pinene initiated by protonic acids, Lewis acids and compound catalysts of protonic acids/Lewis acids under various conditions were discussed in terms of polymerization kinetics, isomerization and product's components. The results show that these three types of catalysts with active species proton (H + ) produced mainly dimer, trimer and tetramer. The compound catalysts of protonic acids/Lewis acids are more active than either one, and the isomerization of α-pinene decreased significantly. It is discovered that a dimer could be synthesized selectively by the compound catalysts with isomerization ratio only 0.5%. Polymer yield and dimer content 99.5% and 83.4% respectively were obtained by the AlCl 3 /CF 3 COOH.