Cavity ring‐down spectroscopy (CRDS) has been applied to characterise different oxide materials (amorphous silica, borosilicate and yttria stabilised zirconia YSZ) which are suitable to be used as support material for size‐selected metal clusters. The sensitivity of the spectroscopic method was improved by means of transversal mode matching and spatial filtering of the laser beam profile, reducing the relative error by 50%. The high sensitivity of CRDS allows the detection of trace amounts of impurities and defect sites in the samples, based on their absorption properties. In YSZ, traces of Nd have been detected. The optical quality of the substrates was determined qualitatively according to the measured optical losses. CRDS surface maps have been used to monitor the homogeneity of the support materials, and the influence of ion bombardment on the surface has been studied. It is shown that in the case of BK7® substrates, sputtering with low energy Ar+ ions could remove deposited gold clusters almost completely causing very low damage to the surface. These results were confirmed analytically.