First-principles molecular dynamics simulation reveals the effects of electronic excitation in the amorphization of Ge-Sb-Te. The excitation makes the phase change an element-selective process, lowers the critical amorphization temperature considerably, for example, to below 700 K at a 9% excitation, and reduces the atomic diffusion coefficient with respect to that of melt by at least 1 order of magnitude. Noticeably, the resulting structure has fewer wrong bonds and significantly increased phase-change reversibility. Our results point to a new direction in manipulating ultrafast phase-change processes with improved controllability.