We report on metal atom segregation within an oxide matrix as a consequence of absorption of short (≂12 ns) excimer laser pulses at 249 nm. The segregation phenomenon is investigated by the example of Au‐TeO2thin films on glass substrates using transient reflectivity and transmissivity techniques as well as ESCA analysis. ESCA depth profiles show drastic modification of the film composition upon laser exposure. Whereas the distribution of Au and TeO2is homogeneous for the as‐deposited films, the laser‐irradiated areas show a total depletion of Au in the surface region exposed to the laser. We interpret this as a laser‐driven segregation of TeO2to the surface and correspondingly of Au towards the substrate. The time‐resolved optical experiments show that the segregation takes place within 30 ns following the laser pulse. The reflectivity and transmissivity changes are characterized by a sharp fluence threshold corresponding to the melting of the film surface.