Cardanol-based benzoxazine (Bz-C) was introduced to a ternary resin system to substitute carboxyl-terminated butadiene–acrylonitrile (CTBN) partially and improve the thermal and dielectric properties of the diglycidyl ether of bisphenol-A (epoxy)/4,4′-diaminodiphenylsulfone (DDS)/CTBN adhesive resin system. The effect of Bz-C on the curing behavior of blends was studied, and factors that affect the thermal, mechanical, and dielectric properties were discussed systematically. Results show that reactions between Ep, DDS, and Bz-C decrease the curing temperature of the quaternary blends and increase the cross-linking densities of the network, leading to higher glass-transition temperature and enhanced mechanical properties. The flexibility of the copolymer films was maintained by the introduction of the aliphatic side chain of Bz-C. Substitution of Bz-C for some group of CTBN in the cross-linked network resulted in decreased dielectric constant and dielectric loss in the copolymer films.