A novel responsive system using a protein-based biopolymer was designed to undergo structural, geometric, and chemical changes upon temperature change or solvent interaction. Poly(γ-glutamic acid) (γ-PGA) is an attractive candidate for various biomedical applications as it is naturally produced, biocompatible and enzymatically degradable. The responsive material was fabricated using an electrospun modified γ-PGA to create a sub-micron fibrous mat. By modulating the environment responsive behaviour in a controlled manner, exciting applications such as wound dressing, compression materials and self-tightening knots are envisaged.