Kalanchoë daigremontiana leaves contain phenolic compounds, which are one of the determinants of plant therapeutic properties. Light and scanning electron microscopes were used to analyse the structure of leaves. The main aims of the study included the analysis of the anatomy of leaves, localisation of phenolic compounds, and identification of phenolic acids. The thickness of the amphistomatic leaf blades, the number, the size of stomata, and the value of stomatal index, as well as the structure of the parenchyma cells have indicated that K. daigremontiana is adapted to arid environments. The histochemical assays revealed the presence of phenolic idioblasts in the leaf blades and petioles. The idioblasts were located in the epidermis, subepidermal layer, a deeper portion of the mesophyll, and in the sheaths of vascular bundles. The phytochemical analyses of leaves demonstrated the presence of gallic, ferulic, caffeic, p-coumaric, and protocatechuic acids in the form of esters. We carried out the research of the anatomical structure of K. daigremontiana leaves, which has been insufficiently documented to date. We have also revealed new localisation of phenolic compounds in the leaf tissues of this species.