With TiCl/MgCl (Ti) and Al(-Bu) (Al) as catalysts, the thermoplastic copolymer of 1-butene(Bt) and 1-hexene(He) was synthesized successfully. The effects of Bt/He, Ti/(He+Bt), Al/Ti, temperature and reaction time on conversion, catalyst efficiency(CE), intrinsic viscosity([η]) and insoluble content were studied. The copolymer was analyzed with Fourier transform-infrared (FTIR) and nuclear magnetic resonance (H-NMR). Results showed that the optimal polymerization conditions were: He/Bt = 0.25, temperature 40ºC–50ºC, Al/Ti = 400–500, Ti/(Bt+He) = 3×10-4*times;10, time 4 h. Intrinsic viscosity was found to increase with increasing Ti/(Bt+He) and decreasing Al/Ti and polymerization temperature. When the molar content of He, Al/Ti and polymerization temperature increased, the insoluble content in CHCl of copolymers decreased. When Ti/(Bt+He) and reaction time increased, the insoluble content in CHCl of copolymers also increased. The crystallization and stereoregularity of poly(1-butene) decreased with the addition of He.