The phase diagrams of Na CO and K CO have been determined with multianvil (MA) and diamond anvil cell (DAC) techniques. In MA experiments with heating, -Na CO is stable up to 12 GPa and above this pressure transforms to /mcm-phase. At 26 GPa, Na CO - /mcm transforms to the new phase with a diffraction pattern similar to that of the theoretically predicted Na CO - /m. On cold compression in DAC experiments, -Na CO is stable up to the maximum pressure reached of 25 GPa. K CO shows a more complex sequence of phase transitions. Unlike -Na CO , -K CO has a narrow stability field. At 3 GPa, K CO presents in the form of the new phase, called K CO -III, which transforms into another new phase, K CO -IV, above 9 GPa. In the pressure range of 9–15 GPa, another new phase or the mixture of phases III and IV is observed. The diffraction pattern of K CO -IV has similarities with that of the theoretically predicted K CO - /m and most of the diffraction peaks can be indexed with this structure. Water has a dramatic effect on the phase transitions of K CO . Reconstruction of the diffraction pattern of -K CO is observed at pressures of 0.5–3.1 GPa if the DAC is loaded on the air.