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The introduction of additive manufacturing technologies in the field of biomaterials science has opened new horizons for regenerative medicine. In this work, we pushed the potential of vat polymerization to the limit for fabricating ultra-porous bioactive SiO2-CaO-MgO-P2O5-CaF2-Na2O glass scaffolds with bone-like architectural characteristics. The tomographic reconstruction of an open-cell foam was used as input file to the printing system and reliably reproduced in all its exquisite details, as assessed by morphological analyses of sintered scaffolds (thickness of single struts 35 μm, exceptionally high porosity around 94 vol%, most pores with size from 500 to 900 μm). Immersion studies in simulated body fluid (SBF) revealed the apatite-forming ability (i.e., in vitro bioactivity) of the scaffolds, the surface of which started being coated by calcium phosphate after just 3 days from the beginning of the experiments. Taken together, these results show great promise for application of such scaffolds in bone defect repair.