Fibre-reinforced polymer structures are often used when stiff lightweight materials are required, such as in aircraft, vehicles and biomedical implants. Despite their very high stiffness and strength 1 , such lightweight materials require energy- and labour-intensive fabrication processes 2 , exhibit typically brittle fracture and are difficult to shape and recycle 3,4 . This is in stark contrast to lightweight biological materials such as bone, silk and wood, which form by directed self-assembly into complex, hierarchically structured shapes with outstanding mechanical properties 5–11 , and are circularly integrated into the environment. Here we demonstrate a three-dimensional (3D) printing approach to generate recyclable lightweight structures with hierarchical architectures, complex geometries and unprecedented stiffness and toughness. Their features arise from the self-assembly of liquid-crystal polymer molecules into highly oriented domains during extrusion of the molten feedstock material. By orienting the molecular domains with the print path, we are able to reinforce the polymer structure according to the expected mechanical stresses, leading to stiffness, strength and toughness that outperform state-of-the-art 3D-printed polymers by an order of magnitude and are comparable with the highest-performance lightweight composites 1,12 . The ability to combine the top-down shaping freedom of 3D printing with bottom-up molecular control over polymer orientation opens up the possibility to freely design and realize structures without the typical restrictions of current manufacturing processes.