Excimer laser sources have already been used with success for a number of novel material processing procedures. Most promising of these deal effectively with challenging materials for which little can be done with ordinary tools in order to materialize their potential. In this presentation, attention is focused on excimer irradiation processing of high grade sintered alumina. On one hand, it is shown how effective and unique can be an excimer beam in transforming the surface of this heavily used material. Under specific irradiation conditions, surface melting of sintered alumina is obtained. The resulting material is then studied by low-angle X-ray diffraction which reveals in particular the eventual formation of the uncommon gamma-alumina phase within 10 nm from the material surface. On the other hand, a rather thorough investigation of the phenomenology of the gamma-phase synthesis is presented, stressing various aspects: dynamic, energetic, structural and chemical, all of them stemming from the unusual characteristics of the excimer laser beam itself. As a result, it is shown how the presence of this gamma-phase may induce direct electroless plating of the excimer- processed alumina surface, on of the many peculiarities of that phase showing potential applications.