Noncentrosymmetric praseodymium calcium oxyborate single crystals, PrCa4O(BO3)3 (PrCOB), were grown by the Czochralski technique. The monoclinic unit cell parameters were found to be a = 8.177 Å, b = 16.157 Å, c = 3.629 Å and Z = 2 with space group Cm. Crystal density was measured using the Archimedes method, being on the order of 3.47 g cm-3. Thermal properties of PrCOB were investigated, where the specific heat was found to be 0.63 J g-1 °C-1 at room temperature, increasing to 0.85 J g-1°C-1 at 700°C. The thermal expansion coefficients were measured to be α11 = 7.99, α22 = 4.90 and α33 = 9.46 (10-6/°C), respectively. In addition, thermal diffusivity λ22 and thermal conductivity κ22 as a function of temperature were studied, where λ22 was observed to decrease from 0.89 to 0.58 mm2 s-1, while κ22 was found to maintain the same value, being ∼1.90 W m-1°C-1 over the temperature range of 20-700°C. © 2013 The Royal Society of Chemistry.