Polymer/graphene composites have attracted much attention for their conductivity and other functions. To control structure of the composites more effectively, we adopted suction filtration combined with the layer-by-layer (LbL) method based on our proposed particle construction method by using polystyrene/graphene (PS/rGO) composite particles as building blocks to prepare PS/rGO composites having a graphene orientation-3D network binary structure. The resulting PS/rGO composites had an excellent conductivity of 1344.3 S/m at a rGO content of 2.10 vol %. Besides, there were always an upgrade in conductivity of the composites along with an improvement of the preparation strategy, from particle constructing, suction filtration, and LbL methods to appropriate adjustment of rGO content in different layers. The results show that there was a clear relationship between the composite structure and the electrical properties and a low efficiency-consumption ratio for both electrical and mechanical properties.