The knowledge of the structural and compositional details of Si/BaSi₂/Si heterostructure annealed at high temperature is a prerequisite for BaSi₂ application in heterojunction thin-film solar cells. For this purpose, Si/BaSi₂/Si heterostructures deposited by magnetron sputtering with different Si layer thickness are submitted to systematic structural and compositional characterizations. Results reveal a BaSi₂/Si heterointerfacial variation caused by surface oxidation and Ba diffusion at the high temperature. Its effects on the optical and electrical properties of Si/BaSi₂/Si heterostructure are presented. The outcomes of this work can be extended to BaSi₂ deposited by other techniques, and generate substantial advantages in BaSi₂ development ranging from improvement on material qualities and eventual deployment in thin-film solar cells.