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BINOL phosphoric acid (BPA) is found to be an efficient cationic organocatalyst for the living ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) with 1-octanol as the initiator.The living nature of the ROP of ε-CL catalyzed by BPA has been confirmed by the linearity of kinetic plot and chain extension experiments.The molar mass of the polycaprolactone (PCL) can be well controlled by varying the initial ratio of ε-CL to 1-octanol.In comparison with other acid organocatalyst,BPA can be used to prepare higher molar mass PCL with narrow molar mass distribution; the highest molar mass of PCL is 4.35 × 104 g/mol with polydispersity index of 1.20.More interestingly,ppm level of BPA is sufficient to catalyze ROP of ε-CL.