Conventional toxic organic solvents used for the fabrication of polymeric membranes are harmful to the environment and human health. Herein, we have investigated Himalayan essential oils (EOs) as green solvents for some polymers. Hit and trial method is used to introduce suitable EOs solvent for the desired polymer to develop thin films and nano/microfibrous membranes. Solvent casting and electrospinning methods are employed to develop polycaprolactone (PCL) thin films and electrospun fibrous membranes, respectively. The physicochemical properties of as-fabricated membranes were investigated using FESEM, TGA, and FTIR spectroscopy. Nano/microfibrous electrospun membranes are successfully developed from PCL using cinnamon oil as a solvent. The antibacterial activity and biocompatibility evaluation revealed that as-fabricated PCL membranes would have high potential in tissue engineering. These findings provide a new platform in the green electrospinning process for the fabrication of nano/microfibrous membranes from a variety of polymers.