Sc-doped semiconductor clusters are the simplest transition metal-and rare-earth metal-doped semiconductor clusters. In this work, the structural evolution behavior and electronic properties of Sc-doped neutral and anionic Si-n (n = 4-16) clusters were studied using the ABCluster global search technique coupled with a hybrid density functional method. The results revealed that although neutral and anionic configurations are different for ScSin (n = 6-14) clusters, the evolution pattern of the ground-state structures is consistent (evolution of linked to encapsulated structures starting from n = 14). The good agreement between the theoretical and experimental photoelectron spectra demonstrated that the obtained anionic global minimum structures are reasonable. The excellent agreement between the adiabatic electron affinities corrected by considering the structural correction factor and the experimental data indicated that the structural correction factor is important for reproducing the experimental data and that the obtained ground-state structures for the neutral ScSin clusters reported herein are reliable. The relative stability and chemical bonding analysis showed that the fully encapsulated ScSi16- cluster is a magic cluster with good thermodynamic and chemical stability.