Chalcogenides, in particular germanium-antimony-tellurium (GeSbTe) and antimony-rich tellurium (R-SbTe) based alloys, are the most technologically significant alloys currently being applied to recordable optical storage as typified by rewritable digital versatile discs (DVD-RW), DVD random access memory, (DVD-RAM). The same alloys are also being applied to nonvolatile random access memory electrical memory in the form of phase change random access memory (PCRAM). In 2004, the phase transition mechanism of GeSbTe was first revealed, demonstrating that the amorphous state is not a random configurational network but is locally well-ordered with the crystalline to amorphous switching process being based upon Ge atoms moving between octahedral and tetrahedral symmetry positions. The kinetic barrier between these two states gives rise to the non-volatile nature of GeSbTe as a storage medium. In contrast, no theoretical analysis has been proposed for SbTe alloys because a Ge-free system. In this paper, the Sb2Te structure has been investigated using the local density approximation (LDA) using a plane-wave basis and compared with experimental results. The effect of external stress on the structure was also investigated. It was found that Sb2Te undergoes two phase-transitions at around 18 GPa (compressive) and −3 GPa (tensile). In the case of negative stress, the c-axis was found to expanded more than the other axes, giving rise a large refractive index change. We report on coherent (uniaxial) melting induced by the breaking a sigma bond between Sb2Te3 and Sb superlattices. We believe this to be the origin of the phase transition that induces a large change in physical properties.