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This invention relates to a process for manufacturing high 1, 4-cis polybutadiene containing hydroxyl groups at ends thereof using molecular oxygen, wherein it comprises the steps of : polymerizing 1, 3-butadiene monomer and butadiene derivatives in the presence of a nonpolar solvent using a transition metal Ziegler-Natta catalyst or a rare earth metal Ziegler-Natta catalyst as a polymerization catalyst to prepare polybutadiene having high 1, 4-cis content of at least 92%; and, introducing hydroxyl groups at the ends of polybutadiene using molecular oxygen as a modifier. With the introduction of hydroxyl groups at the ends of polybutadiene, this invention has the following advantages in that (1) the application scope of high 1, 4-cis polybutadiene can be further widened, and that (2), unlike the conventional method to employ organic or inorganic compound, the use of molecular oxygen as a modifier can ensure any unreacted modifier not to remain in rubber products, and that (3) inexpensive air can be used as the raw material of molecular oxygen.