Butadiene and isoprene were copolymerized with LnCl3–ROH–AIR3 catalytic system. The products obtained were confirmed to be copolymers by their glass transition temperatures and characteristic pyrolytic chromatograms, etc. The equation for copolymerization rate may be expressed as Rp = Kp(M)2(cat). The rate constants of copolymerization, activation energy, and monomer reactivity ratios for catalytic systems containing various rare earth elements in III-B family and different solvents were determined. It was found that the reactivity ratio of butadiene was greater than that of isoprene and r1r2 near 1, and the composition and microstructure of copolymers were not much affected by variation of polymerization conditions. Both monomer repeat units in the copolymers had cis-1,4 contents above 95%, which is a distinguishing feature of coordination polymerization with the lanthanide catalyst system.