Abstract Enhancing the biocompatibility and mechanical stability of small diameter vascular scaffolds remain significant challenges. To address this challenge, small‐diameter tubular structures were electrospun from silk fibroin (SF) from silk textile industry discarded materials to generate bilayer scaffolds that mimic native blood vessels, but derived from a sustainable natural material resource. The inner layer was obtained by directly dissolving SF in formic acid, while the middle layer (SF‐M) was achieved through aqueous concentration of the protein. Structural and biological properties of each layer as well as the bilayer were evaluated. The inner layer exhibited nano‐scale fiber diameters and 57.9% crystallinity, and degradation rates comparable with the SF‐M layer. The middle layer displayed micrometer‐scale fibers diameters with an ultimate extension of about 274%. Both layers presented contact angles suitable for cell growth and cytocompatibility, while the bilayer material displayed an intermediate mechanical response and a reduced enzymatic degradation rate when compared to each individual layer. The bilayer material emulates many of the characteristics of native small‐diameter vessels, thereby suggesting further studies towards in vivo opportunities.