Material ablation by excimer laser micromachining is a promising approach for structuring sol-gel materials as we demonstrate in the present study. Using the well-known direct etching technique, the behaviour of different hybrid organic/inorganic self-made sol-gel materials is examined with a KrF* laser. Ablated depths ranging from 0.1 to 1.5 microm are obtained with a few laser pulses at low fluence (< 1 J/cm(2)). The aim is to rapidly transfer surface relief multi-level diffractive patterns in such a substrate, without intermediate steps. The combination with the 3D profilometry technique of coherence probe microscopy permits to analyse the etching process with the aim of producing multi-level Diffractive Optical Elements (DOE). Examples of four-level DOEs with 10 microm square elementary cells are presented, as well as their laser reconstructions in the infrared.