Lightweight and strong structural materials attract much attention due to their strategic applications in sports, transportation, aerospace, and biomedical industries. Nacre exhibits high strength and toughness from the brick-and-mortar–like structure. Here, we present a route to build nacre-inspired hierarchical structures with complex three-dimensional (3D) shapes by electrically assisted 3D printing. Graphene nanoplatelets (GNs) are aligned by the electric field (433 V/cm) during 3D printing and act as bricks with the polymer matrix in between as mortar. The 3D-printed nacre with aligned GNs (2 weight %) shows lightweight property (1.06 g/cm³) while exhibiting comparable specific toughness and strength to the natural nacre. In addition, the 3D-printed lightweight smart armor with aligned GNs can sense its damage with a hesitated resistance change. This study highlights interesting possibilities for bioinspired structures, with integrated mechanical reinforcement and electrical self-sensing capabilities for biomedical applications, aerospace engineering, as well as military and sports armors.