Electronic transitions in condensed phases are invariably broadened by the variation of local fields: consequently valuable information about the electronic structure is obscured. Several laser techniques, such as spectral hole-burning, fluorescence line narrowing and photon-echo measurements, can overcome this inhomogeneous broadening and it is often possible to increase the spectral resolution by many orders of magnitude and to approach the homogeneous (or natural) linewidth of an electronic origin. Spectral hole-burning is a highly successful laser selective technique that has been applied to a wide range of problems in chemistry, physics and biology. The present chapter reviews recent progress made by hole-burning experiments in the spectroscopy of coordination compounds, in particular chromium(III) complexes.