The machining of several materials such as polymers, metals and ceramics using excimer lasers (193, 248 and 308 nm) was investigated. By photoablation, micrometer resolution can be achieved for polymers if the wavelength and fluence are chosen properly. High-definition processing of metals is complicated by the occurrence of surface melting. An interaction between the ablation plume and the walls of the laser-drilled holes leads to hole widening in the case of polymers at high fluences. For small structures (<100 μm) all materials investigated show a size-dependent ablation rate. This effect has to be taken into account if a precise ablation depth is required for a pattern with structures of different sizes.