In the development of high-performance organic electronics, there has been significant effort in establishing relationships between microstructure and electronic properties, which has provided a deeper understanding of device operation and has guided performance improvements. When considering flexible and stretchable organic electronics, the mechanical behavior of the active layers becomes a critical attribute alongside electronic functionality. Thus, there is a need to establish the role of film morphology on both electronic properties and thermomechanical behavior, and the relationship between mechanical and electronic properties. In this article, we highlight recent advances in establishing these important relationships and the approaches employed to manage film morphology to optimize both mechanical behavior and device performance. Additionally, in stretchable applications, the film morphology may not be static, and capturing the microstructure changes under deformation is necessary to establish structure–property relationships over the expected physical operating space. Thus, also discuss film morphology change under large deformation for various stretchable film approaches.