Mineral carbonation, a process that binds CO2 in the form of carbonates by silicate weathering, is widespread on the Earth's surface. Because of the abundance of silicate rocks and the permanence of the carbonated solids, sequestering CO2 via mineral carbonation has generated lots of interests. However, it is unclear how the fluid‐rock reaction proceeds to completion in spite of an increasing solid volume. We conducted a mineral carbonation experiment in which a sintered olivine aggregate reacted with a sodium bicarbonate solution at reservoir conditions. Time‐resolved synchrotron X‐ray microtomographic images show cracks in polygonal patterns arising in the surface layers and propagating into the interior of the olivine aggregate. The nanotomography data reveal that the incipient cracks intersect at right angles. We infer that stretching due to nonuniform volume expansion generates polygonal cracking of the surfaces. Our data shed new lights on the processes that control hydration and carbonation of peridotite.