A study of electronic, structural and chemical properties of GaAs/ZnSe heterovalent interfaces (HI) in dependence on molecular beam epitaxy (MBE) growth conditions and post-growth annealing was performed. Initial GaAs surface reconstructions ((2×4)As or c(4×4)As) and ZnSe growth mode (MBE or migration-enhanced epitaxy (MEE)) were varied for different undoped and n-doped heterovalent structures. Although all the structures have low extended defect density (less than 10 6 cm −2 ) and rather small (less than 5 nm) atomic interdiffusion at the HI, the structural, chemical and electronic properties of the near-interface area (short-distance interdiffusion effects, dominant chemical bonds, and valence band offset values) as well as electrical properties of the n-GaAs/n-ZnSe heterovalent structures were found to be influenced strongly by the MBE growth conditions and post-growth annealing.