jats:pPhase‐change alloys are the functional materials at the heart of an emerging digital‐storage technology. The GeTe‐Sbjats:sub2</jats:sub>Tejats:sub3</jats:sub> pseudo‐binary systems, in particular the composition Gejats:sub2</jats:sub>Sbjats:sub2</jats:sub>Tejats:sub5</jats:sub> (GST), are one of a handful of materials which meet the unique requirements of a stable amorphous phase, rapid amorphous‐to‐crystalline phase transition, and significant contrasts in optical and electrical properties between material states. The properties of GST can be optimized by doping with p‐block elements, of which Bi has interesting effects on the crystallization kinetics and electrical properties. A comprehensive simulational study of Bi‐doped GST is carried out, looking at trends in behavior and properties as a function of dopant concentration. The results reveal how Bi integrates into the host matrix, and provide insight into its enhancement of the crystallization speed. A straightforward explanation is proposed for the reversal of the charge‐carrier sign beyond a critical doping threshold. The effect of Bi on the optical properties of GST is also investigated. The microscopic insight from this study may assist in the future selection of dopants to optimize the phase‐change properties of GST, and also of other PCMs, and the general methods employed in this work should be applicable to the study of related materials, for example, doped chalcogenide glasses.</jats:p>