Binary, ternary, and quaternary cobalt catalysts for 1,4-transpolybutadiene were prepared, and their reactivity and microstructure were studied. A novel binary catalytic system composed of cobalt adduct (2-PhC6H4O)3Al·Co(OAc)2/AlR3, a ternary system of Co(2-ethylhexanoate)2/AlEt(OPh)2/AlEt3, where OPh is p-dodecyl phenolate, and a quaternary system of cobalt carboxylate·(dialkyl phosphite)/AlR3/(HOPh, p-dodecyl phenol), for high 1,4-transpolybutadiene were compared in polymerization. The binary molecular catalyst, (2-PhC6H4O)3Al·Co(OAc)2/AlR3, was designed as cobalt and aluminum bimetallic form of an intermediate structure in the active site of 1,3-butadiene polymerization for high trans configuration. The bulky ligand, 2-PhC6H4O-, promotes the syn conformation in the active site in favor of trans configuration in polybutadiene. The catalytic activity was reached to 215 kg/(Co mol h) in the quaternary catalytic system. The microstructure consisted of ca. 91% trans, 2% cis and 7% vinyl. Molecular weight was able to be controlled to ca. 700,000 with MWD ca. 2.0. Catalytic reactivity in 1,3-butadiene polymerization was in the order of quaternary > binary > ternary. Diethyl phosphite and triethyl phosphate remarkably reduce molecular weight with high reactivity. The transpolybutadiene prepared by the quaternary catalyst had the glass transition temperature of ca. −80 °C, the melting point of ca. 30 °C, and possessed a low level of crystallinity at room temperature. In the carbon black composite, transpolybutadiene showed superior abrasion resistance, tear strength and chipping resistance to natural rubber, but exhibited high compound Mooney viscosity and low moduli.