Total reflection X-ray fluorescence (TXRF) is a novel variant of energy dispersive X-ray fluorescence (EDXRF) with one significant geometric difference between them. Synchrotron Radiation is probably the most highlighted development in the field of TXRF which has opened up new analytical aspects of hyphenated techniques such as TXRF-X-ray absorption fine structures (TXRF-XAFS) which not only provides information of elemental concentration but also on speciation, local atomic and electronic structures of materials. Novel sample preparation and preconcentration approaches have also contributed significantly in increasing the analytical sensitivity and precision. These include dispersive liquid-liquid micro-extraction (DLLME), cloud point extraction (CPE), hollow fiber liquid phase microextraction (HF-LPME), etc. Further, use of membranes and nanomaterials for sample preconcentration have drastically improved the TXRF detection limits from picogram to femtogram level thereby, making it an excellent micro-analytical technique for analysis of micro-samples. Micro-TXRF is another upcoming variant of TXRF leading to elemental profiling at trace levels in the field of medical, biological, environmental, archeological, industrial and forensics.