Recently, all-optical memory and optical-computation properties of phase-change materials are receiving intensive attention. Because writing/erasing information in these devices is usually achieved by laser pulses, the interaction between the laser and the phase-change materials becomes a key issue for such new applications. In this work, by a time-dependent density-functional theory molecular-dynamics study, the physics underlying the optical excitation induced amorphization of Sc-Sb-Te is revealed, which goes back to superatom-like Sc-centered structural motifs. These motifs are found to be still robust under the excitation. A selected occupation of the Sc d-t 2g orbitals (as a result of optical excitation) leads to a significant change of Sc-centered bond angles. In addition, the especially weak Sb-Te bonds next to the Sc motifs are further diminished by excitations. Therefore, the Sc-centered motifs can promote breaking, switching, and reforming of the surrounding Sb-Te network and, therefore, facilitate the amorphization of Sc-Sb-Te. The study shows the unique role of Sc-centered motifs in optically induced phase transition, and displays potential applications of Sc-Sb-Te alloys in optical memory/computation. npj Computational Materials (2020) 6:31 ; https://doi.