Herewith, we report on the first observation of coherent phonons in alexandrite crystal obtained by means of the femtosecond Optical Kerr Effect spectroscopy. We have managed to observe dynamics of the Raman-active modes with high resolution and to find their lifetimes in the temperature range between 263 K and 373 K. We have used the obtained temperature dependence of phonon lifetimes and frequencies for calculation of the anharmonic coupling constants. On the basis of our results, we have also calculated the widths of homogeneously broadened Raman lines. Our results prove that, in case of transparent samples, this experimental technique is a very good alternative to the commonly used transient reflection method. Copyright © 2013 John Wiley & Sons, Ltd.