Abstract: Using polystyrene, divinylbenzene (DVB) as main raw materials, cross-linked polystyrene (CLPS) block material was prepared by a novel method of γ-ray radiation polymerization. The sample was tested and characterized by FT-IR, DSC, TG and DMA, etc. Results show that when DVB mass fraction is more than 1% and the absorb dose is 150~200 kGy, the transparent and zero defect sample can be synthesized in nitrogen atmosphere. The glass transition temperature increased slowly as the increasing of DVB mass fraction in the copolymer. The glass transition temperature can reach 127 ℃, and the sample can be stable until 380 ℃. Meanwhile, the tensile strength and the elongation at break of CLPS firstly increase and then decrease with the increasing of DVB mass fraction, and the maximum is present at 1.6%~1.8% of DVB mass fraction, showing good mechanical properties. The dielectric constant is stable about 2.48~2.50 at 9.3 GHz, and the dielectric dissipation factors are extremely low with the value of 4×10-4～6×10-4.