The principle to utilize total reflection of the primary X-rays in fluorescence analysis is known since a lot of years. Nevertheless, analytical chemistry did not profit from the inherent advantages of the method for a long time. The main reason for this failure was the lack of instruments which were easy to use in practice. A few years ago, however, the development of a proper mechanical design and of adapted sample preparation techniques led to commercially available spectrometers which throughout fulfill the demands for routine applications. Since then the utilization of Total-Reflection X-Ray Fluorescence Analysis (TXRF) has increased rapidly. The scope of work is meanwhile widespread over environmental research and monitoring, mineralogy, mineral exploration, oceanography, biology, medicine and biochemistry. Accordingly, numerous matrices have been handled.