Three-dimensional (3D) ferroelectric materials are promising electromechanical building blocks for achieving human-machine interfacing, energy sustainability, and enhanced therapeutics. However, current natural or synthetic materials cannot offer both high piezoelectric responses and desired mechanical toughness at the same time. Here, a nacre-mimetic ferroelectric metamaterial was created with a ceramic-like piezoelectric property and a bone-like fracture toughness through a novel low-voltage-assisted 3D printing technology. The one-step printed bulk structure, consisting of periodically intercalated soft ferroelectric and hard electrode intercalated layers, exhibited a significantly enhanced longitudinal piezoelectric charge coefficient of over 150 pC N-1, as well as a superior fracture resistance of ~ 5.5 MPa·m1/2 more than three times higher than piezo-ceramics. The excellent printability together with the unique combination of both high piezoelectric and mechanical behaviors allowed us to create bone-like structure with tunable anisotropic piezoelectricity and bone-comparable mechanical properties, marking a cornerstone toward manufacturing practical, high-performance, and smart biological systems.