Thermoelectrically cooled semiconductor detectors, such as Si-PIN, Si-drift, Cd 1−x Zn x Te and HgI 2 , coupled to miniaturized low-power X-ray tubes, are well suited in portable systems for energy-dispersive X-ray fluorescence (EDXRF), analysis of archaeological samples. The Si-PIN detector is characterized by a thickness of about 300 μm, an area of about 2×3 mm 2 , an energy resolution of about 200–250 eV at 5.9 keV and an entrance window of 25–75 μm. The Si-drift detector has approximately the same area and thickness, but an energy resolution of 155 eV at 5.9 keV. The efficiency of these detectors is around 100% from 4 to 10 keV, and then decreases versus energy, reaching ∼9% at 30 keV. Coupled to a miniaturized 10 kV, 0.1 mA, Ca-anode or to a miniaturized 30 kV, 0.1 mA, W-anode X-ray tubes, portable systems can be constructed, which are able to analyse K-lines of elements up to about silver, and L-lines of heavy elements. The Cd 1− x Zn x Te detector has an area of 4 mm 2 and a thickness of 3 mm. It has an energy resolution of about 300 eV at 5.9 keV, and an efficiency of 100% over the whole range of X-rays. Finally the HgI 2 detector has an efficiency of about 100% in the whole range of X-rays, and an energy resolution of about 200 eV at 5.9 keV. Coupled to a small 50–60 kV, 1 mA, W-anode X-ray tube, portable systems can be constructed, for the analysis of practically all elements. These systems were applied to analysis in the field of archaeometry and in all applications for which portable systems are needed or at least useful (for example X-ray transmission measurements, X-ray microtomography and so on). Results of in-field use of these detectors and a comparison among these room temperature detectors in relation to concrete applications are presented. More specifically, concerning EDXRF analysis, ancient gold samples were analysed in Rome, in Mexico City and in Milan, ancient bronzes in Sassari, in Bologna, in Chieti and in Naples, and sulfur (due to pollution) in an old roman fresco in the church of S. Stefano Rotondo (Rome).