Polymer/graphene composite films with a nacre-like layered structure have been extensively researched. However, most composites have been prepared using a small amount of graphene up to now, which extremely restricts the mechanical and electrical properties. Herein, a series of polymers (HEC, HPMC, and PVA)/graphene layered composites with high-content graphene (from 45 to 75%) are prepared by simple solution evaporation and then reduction method. The mechanical and electrical properties of these composites are studied. Mechanical results show with the increase of graphene oxide (GO) content, the tensile strength increases, and later decreases. Electrical performance indicates that the electrical conductivity of HPMC/rGO is greater than both HEC/rGO and PVA/rGO. Considering mechanical and electrical performance, HPMC/rGO-65 with 65% graphene content is better than others, and its tensile strength and the conductivity are 32.08 MPa and 0.63 S/m, respectively. This work provides a new strategy for developing biomimetic nacre-like composites with high graphene content, which could improve the comprehensive properties of polymer/graphene.