This work on the botanical origin of various types of honey produced in Slovenia and based on the mineral content analyses by the total reflection X-ray spectrometry (TXRF) is a continuation of this group's preliminary work (Golob, T.; Doberšek, U.; Kump, P.; Nečemer, M. Food Chem. 2005, 91, 593-600), which introduced the analytical methodology and employed only a simple statistical evaluation and which examined the possibility to determine the botanical origin of honey samples via elemental content. A much more comprehensive study on a total of 264 major types of honey samples harvested in 2004, 2005, and 2006 and interpreting the results with up to date chemometric methods was performed in this work. Slovenia is a small country by surface area, but it is pedologically and climatically diverse, therefore offering interesting possibilities for studying the influence of these diversities on the elemental content of natural products. By employing principal component analysis (PCA) and regularized discriminant analysis (RDA) it was established that from all of the measured elements only the four characteristic key elements Cl, K, Mn, and Rb could be used to best discriminate the types of honey. It was established that the employed combination of a simple, fast, and inexpensive multielement TXRF analytical approach and the evaluation of data by chemometric methods has the potential to discriminate the botanical origins of various types of honey.