Compared with traditional phenolic resins, benzoxazine resin exhibits numerous advantages, such as flexible molecular structure design, no small molecules released in curing process, excellent thermal and mechanical stability and high char yield, which make it to be the important candidate for the electronic communication industry. With development of the next generation high density and high speed integrated circuits, the design and development of low dielectric thermosetting resins have recently attracted widespread attention. This paper reviewed the synthesis and modifications of benzoxazine resins, with particular emphasis on the low dielectric properties. Firstly, it presented an overview of design, preparing and characterizing the novel benzoxazines. Secondly, it concentrated on benzoxazine based organic-inorganic nanocomposites. Thirdly, the preparation method and dielectric properties of binary, ternary and tetra-copolymer systems based on benzoxazine resins were discussed.