•Temperature and reactant concentration interacted to define the precipitated phase.•DCPD/OCP mixtures (22 °C) and HAP (45 °C) were obtained under low concentration.•DCPD (22 °C) and DCPD/OCP (45 °C) precipitated under medium and high concentrations.•Particle hydrodynamic radius was not strongly affected by the tested variables.•Surface area results reflected differences in particle morphology among phases. Calcium orthophosphates (CaP) constitute an important group of biomaterials used in bone repair and tooth remineralization. In some applications, controlling particle surface area and/or dimensions is important to fine-tune ion release kinetics. This study evaluated the interaction between synthesis temperature (22 °C or 45 °C) and reactant concentration (“Low”: 0.1 mol.L−1, “Medium”: 0.5 mol.L−1 or “High”: 1.0 mol.L−1) on phase formation, particle morphology, size and surface area. Calcium and phosphate precursor solutions (Ca/P = 1.0, initial pH: 7.9–8.1) were mixed and the precipitate was obtained after 24 h. DCPD (CaHPO4·2H2O) was the only phase identified by X-ray diffraction at 22 °C/Medium and 22 °C/High, with large plate crystal morphology, while DCPD/OCP (Ca4H(PO4)3·2.5H2O, as agglomerates of sub-micron crystals) mixtures were observed at 22 °C/Low, 45 °C/Medium and 45 °C/High. Small-plate, low-crystallinity HAP (Ca5OH(PO4)3) was obtained at 45 °C/Low. In spite of the different morphologies, particle hydrodynamic radius (as determined by laser light scattering) was not affected by the tested variables (median: 10–20 μm). Surface area, on the other hand, varied according to particle morphology (37–135 m2/g). In conclusion, temperature and reactant concentration interacted to define the precipitated phases, each of them with a characteristic morphology. Thermodynamically more stable phases (OCP or HAP) were found in syntheses conducted at 45 °C due to accelerated DCPD hydrolysis.