Electrospinning is a highly versatile technique for fabricating nanofibrous membranes with high surface-area-to-volume ratios and tunable porosity. Although polycaprolactone (PCL) is widely utilized in biomedical engineering due to its biocompatibility, its electrospinning traditionally relies on hazardous organic solvents like dichloromethane (DCM) and N,N-dimethylformamide (DMF). This paper details the development of a fully sustainable, green electrospinning process for PCL using a bio-derived binary mixture of acetic acid and formic acid. Processing parameters (applied voltage, tip-to-collector distance, and flow rate) were systematically optimized using a Design of Experiments (DoE) response surface methodology. Scanning electron microscopy (SEM) confirmed the successful fabrication of uniform, bead-free nanofibers with a mean diameter of 247 nm, representing a 37.3% reduction compared to conventional DCM:DMF-spun matrices. Fourier-transform infrared spectroscopy (FTIR) verified complete solvent evaporates.