Silk is a natural polymer with a broad range of potential applications in textiles, advanced materials, biomedical devices, and drug delivery. The ability to control the morphology and assembly of silk fibroin is essential for the fabrication of silk-based structured materials. Here, we report an effective and simple approach based on droplet dissolution for weaving silk fibroin into spheres of several hundred micrometers in diameter. The spheres possess regular wrinkled microstructures on the surface and switchable transparency for visible light. To produce these silk spheres, we immersed a sessile microdrop of the silk fibroin aqueous solution in a surrounding phase of ethanol in toluene at low concentration (<10%). The droplet experienced a two-phase process: the first phase of volume expansion due to the intake of organic solvents from the surrounding phase and the second phase of droplet dissolution. The dissolution rate is closely related to the dynamics of the droplet, while the resulting microstructure of the silk microsphere is simply adjusted by the composition of the surrounding solution. At high concentrations of ethanol, silk fibroin formed a thin shell around the droplet during the initial expansion of the droplet in volume. As the droplet shrank at a later stage, the shell around the droplet wrinkled and crumpled, leading to regular ridges and crevices on the microsphere surface. This work demonstrates that controlled droplet dissolution may be explored as a novel and effective way to tailor microstructures of silk assemblies. The as-prepared silk microspheres may be potentially used as optical units or microcarriers.