In situ reflectivity measurements of the solid/liquid interface with a pump-probe setup were performed during laser-induced backside wet etching (LIBWE) of fused silica with KrF excimer laser using toluene as absorbing liquid. The intensity, the temporal shape, and the duration of the reflected light measured in dependence on the laser fluence are discussed referring to the surface modification and the bubble formation. The vaporisation of the superheated liquid at the solid interface causes a considerable increase of the reflectivity and gives information about the bubble lifetime. The alterations of the reflectivity after bubbles collapse can be explained with the changed optical properties due to surface modifications of the solid surface. Comparative studies of the reflectivity at different times and the etch rate behaviour in dependence on the laser fluence show that the in situ measured surface modification begins just at the etch threshold fluence and correlates further with etch rate behaviour and the etched surface appearance. The already observed surface modification at LIBWE due to a carbon deposition and structural changes of the near surface region are approved by the changes of the interface reflectivity and emphasizes the importance of the modified surface region in the laser-induced backside wet etching process. (c) 2005 Elsevier B.V. All rights reserved.