AbstractDoping is indispensable to tailor phase-change materials (PCM) in optical and electronic data storage. Very few experimental studies, however, have provided quantitative information on the distribution of dopants on the atomic-scale. Here, we present atom-resolved images of Ag and In dopants in Sb₂Te-based (AIST) PCM using electron microscopy and atom-probe tomography. Combing these with DFT calculations and chemical-bonding analysis, we unambiguously determine the dopants’ role upon recrystallization. Composition profiles corroborate the substitution of Sb by In and Ag, and the segregation of excessive Ag into grain boundaries. While In is bonded covalently to neighboring Te, Ag binds ionically. Moreover, In doping accelerates the crystallization and hence operation while Ag doping limits the random diffusion of In atoms and enhances the thermal stability of the amorphous phase.