Combined high strength and toughness of film materials are rather important for their industrial applications. As a new class of films, graphene oxide films (GOFs) attract intense attention in many applications but are frequently divergent, inconsistent, and poorly reproducible in their mechanical properties. In this study, we first demonstrate that different chemical compositions and assembly structures probably are responsible for the difference in elongations between cast GOFs and filtration GOFs. Comprehensive analysis of the morphologies and mechanical properties indicates that the enhanced elongation of the thick cast GOFs is mainly attributed to the presence of a unique skin-wrinkles-skin structure, which more easily forms in cast GOFs than in filtration counterparts. On the basis of this finding, we attempt to optimize the strength-toughness performance of the cast GOFs by adjusting their structures. With an appropriate thickness of 12.5 μm, the GOFs can achieve an ultrahigh toughness up to 4.37 MJ m(-3), which is even comparable to the polymer-toughening graphene/GO-based paper-like materials. Such an optimization of the mechanical properties from the perspective of skin-wrinkles-skin structure appears to be a universal approach that could be extended to a variety of other film materials.