Optical nanofibrous sensors show potential in many application areas, including biomedicine, as they provide ultra-sensitivity combined with versatility, flexibility and user-friendliness. In our work stimuli-sensitive dyes are incorporated in a polymeric nanofibrous matrix by the process of solvent electrospinning. An important challenge that is tackled here is dye-immobilization as to design a stable sensor. In addition, an ecological friendly production process is aimed for resulting in the use of “green” solvents such as water and ethanol. However, the use of hydrophilic polymers poses some challenges with regard to the solvent electrospinning process, which are addressed in this work as well.