Silk sericin (SS) has been extensively used to fabricate scaffolds for tissue engineering. However, due to its inferior mechanical properties, it has been found to be a poor choice of material when being electrospun into nanofibrous scaffolds. Here, SS has been combined with poly(vinyl alcohol) (PVA) and electrospun to create scaffolds with enhanced physical properties. Crucially, these SS/PVA nanofibrous scaffolds were created using only distilled water as a solvent with no added crosslinker in an environmentally friendly process. Temperature has been shown to have a marked effect on the formation of the SS sol–gel transition and thus influence the final formation of fibers. Heating the spinning solutions to 70 °C delivered nanofibers with enhanced morphology, water stability and mechanical properties. This is due to the transition of SS from β‐sheets into random coils that enables enhanced molecular interactions between SS and PVA. The most applicable SS/PVA weight ratios for the formation of nanofibers with the desired properties were found to be 7.5/1.5 and 10.0/1.5. The fibers had diameters ranging from 60 to 500 nm, where higher PVA and SS concentrations promoted larger diameters. The crystallinity within the fibers could be controlled by manipulation of the balance between PVA and SS loadings. In vitro degradation (in phosphate buffer solution, pH 7.4 at 37 °C) was 30–50% within 42 days and fibers were shown to be nontoxic to skin fibroblast cells. This work demonstrates a new green route for incorporating SS into nanofibrous fabrics, with potential use in biomedical applications. © 2019 Society of Chemical Industry