Wool keratin is a natural material with excellent properties, which is considered as scaffold biomaterial for tissue engineering. Polyethylene glycol can improve the mechanical properties of keratin materials because of its excellent biocompatibility and plasticity. In the present work, poly (ethylene glycol) methyl ether methacrylate (MPEGMA) was grafted onto keratin by thiol‐ene photoclick reaction. The results of FTIR and SDS‐PAGE verified the successful reaction between MPEGMA and keratin. Compared with the keratin, circular dichroism and XRD results showed that the β‐sheet ratio increased in MPEG‐g‐keratin. Additionally, it can be found that the exposure of keratin hydrophobic amino acids increased quickly and the micelle size became larger due to the introduction of MPEG from the results of fluorescence spectroscopy and particle size analysis. The MPEG‐g‐ keratin was formed into a membrane to further study the application of the modified keratin. Compared with the keratin membrane, the flexibility and biocompatibility of modified keratin have been improved. This work provides an eco‐friendly and facile approach for preparation of the keratin biomaterials.