The recent increase in the development of polymer-based technological devices has necessitated a surge in associated fabrication strategies. An adequate understanding of the interfacial properties in such systems is required to meet the challenges inherent to these applications, ranging from electronics to biomedicine. In this work, utilize thermal reflow to investigate the interfacial properties of multilayer silk fibroin film constructs We demonstrate that reflow can be utilized to control the water content, glass transition, and beta sheet crystallinity of such constructs, leading to control of the mechanical properties at the interface. Such analysis may lend insight into the interfacial properties of similar semicrystalline biopolymers, increasing the number of fabrication options for the development of devices at the biological-technological nexus.