In an integrated circuit, signal propagation loss is proportional to the frequency, dissipation factor (Df), and square root of dielectric constant (Dk). The loss becomes obvious as we move to high-frequency communication. Therefore, a polymer having low Dk and Df is critical for copper-clad laminates at higher frequencies. For this purpose, a 4-vinylbenzyl ether phenoxy-2,3,5,6-tetrafluorophenylene-terminated OPE (VT-OPE) resin was synthesized and its properties were compared with the thermoset of commercial OPE-2St resin. The thermoset of VT-OPE shows a higher Tg (242 vs 229 °C), a relatively high cross-linking density (1.59 vs 1.41 mmole cm–3), a lower coefficient of thermal expansion (55 vs 76 ppm/°C), better dielectric characteristic at 10 GHz (Dk values of 2.58 vs 2.75, Df values of 0.005 vs 0.006), lower water absorption (0.135 vs 0.312 wt %), and better flame retardancy (UL-94 VTM-0 vs VTM-1 with dropping seriously) than the thermoset of OPE-2St. To verify the practicability of VT-OPE for copper-clad laminate, a laboratory process was also performed to prepare a copper-clad laminate, which shows a high peeling strength with copper foil (5.5 lb/in), high thermal reliability with a solder dipping test at 288 °C (>600 s), and the time for delamination of the laminate in thermal mechanical analysis (TMA) at 288 °C is over 60 min.