A key challenge in developing bioinspired composites is the fabrication of well-defined 3D hierarchical structures ranging from nano to the macroscale. Herein, the development of a synthetic polymer–apatite composite realized by integrating bottom-up self-assembly and additive manufacturing (AM) is described. The resulting composite exhibits a bioinspired hierarchical structure over its 3D macroscopic volume. The composite is assembled in a bottom-up manner, where periodic nanoscale assemblies of organic micellar fibrils and inorganic apatite nanocrystals are organized as bundles of mineralized microstructures. These microstructural bundles are preferentially oriented throughout the macroscopic volume of the material via extrusion based AM. The obtained structural hierarchy is investigated in 3D using electron microscopy and small angle X-ray scattering tensor tomography and correlated to the structural hierarchy and anisotropy observed in biological tissues such as bone and the bone–cartilage interface. This work demonstrates the possibility to form polymer–apatite composites with a well-defined hierarchical structure throughout its macroscopic volume, which is crucial for the development of mechanically optimized materials for applications such as bone and osteochondral implants.