We report the first study of the application of excimer lasers in dentistry for the treatment of dental root canals. High-energy ultraviolet (UV) radiation emitted by an XeCl excimer laser (308 nm) and delivered through suitable optical fibers can be used to remove residual organic tissue from the canals. To this aim, UV ablation thresholds of dental tissues have been measured, showing a preferential etching of infiltrated dentin in respect to healthy dentin, at laser fluences of 0.5-1.5 J/cm2. This technique has been tested on extracted tooth samples, simulating a clinical procedure. Fibers of decreasing core diameters have been used to treat different sections of the root canal down to its apical portion, resulting in an effective, easy, and fast cleaning action. Possible advantages of excimer laser clinical applications in respect to usual procedures are also discussed.