This study evaluated the biocompatibility and accuracy of 3D-printed β-tricalcium phosphate (β-TCP) pure ceramic scaffolds. A specific shaping process associating a digital light processing (DLP) 3D printer and a heat treatment was developed to produce pure β-TCP scaffolds leaving no polymer binder residue. The β-TCP was characterised using X-ray diffraction, infrared spectroscopy and the detection of pollutants. The open porosity of produced matrices and their resorption were studied by hydrostatic weighing and calcium release measures. The biocompatibility of the printed matrices was evaluated by mean of osteoblast cultures. Finally, macroporous cubic matrices were produced. They were scanned using a micro-Computed Tomography scanner (micro-CT scan) and compared to their numeric models. The results demonstrated that DLP 3D printing with heat treatment produces pure β-TCP matrices with enhanced biocompatibility. They also demonstrated the printing accuracy of our technique, associating top-down DLP with the sintering of green parts. Thus, this production process is promising and will enable us to explore complex phosphocalcic matrices with a special focus on the development of a functional vascular network.