The synthesis of high molecular weight star-shaped polymers comprising poly(1,3-cyclohexadiene) arms coupled to a divinylbenzene (DVB) core is reported. In-situ FTIR spectroscopy was used to verify first-order polymerization kinetics for 1,3-cyclohexadiene at 40 degreesC in cyclohexane with a 10 wt % monomer concentration using a tetramethylethylenediamine (TMEDA) to n-butyllithium (n-BuLi) ratio of 5/4. The propagation rate constant was determined to be 0.31 L mol(-1) s(-1). The degree of 1,2-addition (70%) vs 1,4-addition (30%) for 1,3-cyclohexadiene was determined using H-1 NMR spectroscopy. The molecular weights of the preformed arms were 10 000 and 5000 g/mol, and the ratio of DVB to n-BuLi was systematically varied from 6:1 to 24:1. Gel permeation chromatography coupled with light scattering detection was utilized to detect the formation of star-shaped polymers and the presence of star-star coupling. In-situ spectroscopy and obvious color changes indicated that the addition of DVB to poly(1,3-cyclohexadienyllithium) was rapid. The molecular weight distribution (M-W/M-n) of the star polymers ranged from 1.4 to 1.9. The polymeric materials were thermally stable to 330 degreesC under a nitrogen environment. The refractive indices of both the homopolymers and star polymers were 1.572 at 600 nm and remained relatively constant from 1600 to 550 nm. The T-g of the high molecular weight star-shaped polymers was 150 degreesC.