The first direct picosecond time‐resolved measurement of the nonradiative transition dynamics between the excited4T2pump band and the metastable2Estorage level of the trivalent chromium ion in alexandrite is reported. The nonradiative relaxation times of 17 ps for intra‐4T2vibrational transitions, and 27 ps for4T2→2Eelectronic transition are obtained. The thermal repopulation rate of the4T2state from the metastable2Elevel is of the order 3.5×109s−1.