An overview of the basic mechanisms of IR laser ablation of dental enamel is presented. Enamel is a highly structured tissue consisting of an heterogeneous distribution of water, mineral, protein and lipid. Absorption bands of water and carbonated hydroxyapatite can be selectively targeted from 2.7 to 11-micrometer via several laser wavelengths. Mechanistic differences in the nature of ablation and the varying surface morphology produced can be explained by the microstructure of the tissue. Suggested criteria for the choice of the optimum laser parameters for clinical use, the influence of plasma shielding and the role of exogenous water on the mechanism of ablation are discussed.