Ge–Sb–Te alloys are widely used for data recording based on the rapid and reversible amorphous-to-crystalline phase transformation that is accompanied by increases in the optical reflectivity and the electrical conductivity. However, uncertainties about the optical band gaps and electronic transport properties of these phases have persisted because of inappropriate interpretation of reported data and the lack of definitive analytical studies. In this paper we characterize the most widely used composition, Ge2Sb2Te5, in its amorphous, face-centered-cubic, and hexagonal phases, and explain the origins of inconsistent or unphysical results in previous reports. The optical absorption in all of these phases follows the relationship αhν∝(hν-Egopt)2, which corresponds to the optical transitions in most amorphous semiconductors as proposed by Tauc, Grigorovici, and Vancu [Tauc etal, Phys. Status Solidi 15, 627 (1966)], and to those in indirect-gap crystalline semiconductors. The optical band gaps of the amorphous, face-centered-cubic, and hexagonal phases are 0.7, 0.5, and 0.5 eV, respectively. The subgap absorption in the amorphous phase shows an exponential decay with an Urbach slope of 81 meV. We measured the photoconductivity of amorphous Ge2Sb2Te5 and determined a mobility-lifetime product of 3×10-9 cm2/V. The spectral photoconductivity shows a threshold at about 0.7 eV, in agreement with our analys- is of the optical band gap. The face-centered-cubic and hexagonal phases are highly conductive and do not show freeze-out; even at 5 K the density of free carriers remains at 1019–1020 cm-3, so these are degenerate semiconductors in which the Fermi level resides inside a band. In the hexagonal phase, the effect of free electrons on the Hall coefficient is significant at high temperatures. When the Hall data are fitted using the two-carrier analysis, the hole mobility is found to decrease slowly with temperature, as expected. The considerations discussed in this paper can be readily applied to study related chalcogenide materials.