The purpose of the study is to design and prepare new conductive composites with both electrical and magnetic functions. The chopped carbon fiber (CF) with good conductivity and chopped Ni-plated CF (Ni-CF) with both magnetic and conductive properties were used as the functional body. The chopped glass fiber (GF) was used as the filler, the vinyl ester resin (VER) was used as the matrix, and the electromagnetic properties can be controlled. The effects of CF content on the volume resistivity of CF-GF/VER conductive composites were studied. The effects of Ni-CF length on the volume resistivity of (Ni-CF)-CF-GF/VER were also investigated. The effects of Ni-CF content on the volume resistivity of the composites were investigated. The volume resistivity and magnetic permeability, and the electromagnetic shielding performance of conductive composite material were preliminarily explored. The results show that the volume resistivity is adjustable from 0.35 to 36.48 Ω·cm, and the permeability is adjustable from 0.2 to 0.7. The CF and Ni-CF content and length will have a great influence on the electromagnetic properties of (Ni-CF)-CF-GF/VER conductive composites. The prepared (Ni-CF)-CF-GF/VER conductive composites are expected to be used in the field of electromagnetic shielding.