The controlled assembly of matter at the nanoscale is leading to a broad spectrum of new functional materials with emergent collective properties. Oftentimes, however, self-assembled materials are affected by poor mechanical performance. A promising solution against this backdrop has been found in the tailored combination of multiple constituents into hierarchically structured hybrid materials. We present here the case of ceramic-organic nanocomposites featuring a periodic superlattice, i.e. supercrystallinity. Strategies for strengthening, stiffening, hardening and toughening these nanoarchitected materials are highlighted, via a combination of ex- and in-situ high resolution microscopy and synchrotron studies, supported by finite-element simulations.