Ceramics with pores comprising multiple scales have many desirable properties and are naturally found in some natural materials such as porous carbonate rocks, coral reefs, and bones. There is a great interest in mimicking such hierarchical porosity using calcium carbonate for applications such as bone scaffolds, artificial corals, and rock replicas for petrophysical and geomechanical tests. However, it is difficult to control the porosity at multiple scales using a single manufacturing process. On the one hand, the traditional routes to produce macroporous ceramics (such as sacrificial template, template replica, and direct foaming) have limited control over pore size, distribution, and geometry. Therefore, 3D printing has been considered a promising alternative to achieve high reproducibility and design freedom for pore geometry. However, it is typically restricted to large pores (>100 µm) due to printing resolution. For calcium carbonate, there is an additional challenge: its thermal decomposition at temperatures below the expected sintering temperature. This study proposes a methodology to produce calcium carbonate parts with hierarchical porosity by using additive manufacturing (vat-photopolymerization) to produce the larger pores (>200 µm) combined with sacrificial pore formers to produce the smaller pores. The methodology was divided into five steps. 1) We selected the sacrificial pore formers among some potential candidates, including sucrose, ammonium bicarbonate, and PMMA. The selection considered the particle size, density, decomposition temperature (evaluated by TGA/DSC), and compatibility with the acrylate photocurable resin. 2) Photocurable suspensions of calcite (CaCO₃) were formulated with different porogen contents, aiming at achieving 5, 10, and 20 vol% of induced pores. Then, the suspensions were characterized concerning their rheology, stability, and photosensitive parameters. The solid content of calcite and the amount of dispersant were adjusted to achieve good printability. 3) The optimized suspension was printed through vat-photopolymerization. The printing process was optimized by adjusting the layer thickness and exposure time. The minimum features of the printed parts (holes, channels, and struts) were analyzed with SEM. 4) The debinding of the printed parts was performed in the air atmosphere. The temperatures and heating rates of the sintering process were optimized based on the TGA/DSC of the samples. The sintering was performed in a CO₂ atmosphere up to 850°C to avoid the decomposition of the calcite into calcium oxide. The crystalline phases presented after sintering were evaluated with X-ray diffraction. The microstructure and defects (such as delamination and cracking) caused by the thermal treatment were assessed, and the maximum wall thickness was determined. 5) Finally, the parts were characterized concerning their microstructure, mechanical strength, density, and porosity. The presented methodology significantly contributes to the manufacturing of porous calcium carbonate parts. The applicability of the produced samples as rock replicas, artificial corals, and bone scaffolds was discussed, highlighting the advantages and current limitations of the presented methodology.