We investigated the behavior of MnCO3 in the pressure range 0–50 GPa and ambient temperature by synchrotron X-ray single-crystal diffraction technique. MnCO3 maintains the calcite-type structure (R3̄c symmetry) up to 44 GPa. Above this pressure we observed a phase transition. The high-pressure phase, MnCO3-II, is triclinic, with cell parameters a = 2.928(2), b = 4.816(4), c = 5.545(4) Å, α = 101.71(6)°, β = 94.99(6)°, γ = 89.90(6)°, and V = 76.28(10) Å3 at 46.8 GPa. The structure is solved with the charge flipping algorithm. MnCO3-II is isostructural with CaCO3-VI. The density increase on phase transition is 4.4%. The occurrence of CaCO3-VI structure in MnCO3 composition indicates that CaCO3-VI structure is also adopted by carbonates with cations smaller than calcium.