We investigate the role of interface initiation conditions on the growth of ZnSe/GaAs heterovalent heterostructures. ZnSe epilayers were grown on a GaAs surface with various degrees of As-termination and the application of either a Zn or Se pre-treatment. Structural analysis revealed that Zn pre-treatment of an As-rich GaAs surface suppresses Ga2Se3 formation at the interface and promotes the growth of high crystal quality ZnSe. This is confirmed with low-temperature photoluminescence. However, moderation of Ga-Se bonding through a Se pre-treatment of an As-rich GaAs surface can prevent excessive intermixing at the interface and promote excitonic emission in the underlying GaAs layer. These results provide guidance on how best to prepare heterovalent interfaces for various applications. (C) 2017 Elsevier B.V. All rights reserved.