The demand for biobased nonwoven-like fibers with enhanced durability is growing, particularly in fields such as tissue engineering, air filtration and protective textiles. Micro- and nanofibrous materials, with their high surface area, porosity, and 3D structure, offer excellent performance in these applications. However, many require greater mechanical strength, thermal stability, and longevity. Polylactic acid (PLA) is a promising biobased polymer, but its limited strength, heat resistance, and hydrolytic stability hinder its broader use. A potential solution is stereocomplex PLA (scPLA), formed by blending the two enantiomers, poly(L-lactic acid) (PLLA) and poly(D-lactic acid) (PDLA). The strong hydrogen bonding and dipole–dipole interactions between these enantiomers result in stereocomplex (SC) crystallites, enhancing mechanical, thermal, and thermo-mechanical properties compared to conventional PLA, making it a viable engineering thermoplastic. While solution electrospinning has been explored for scPLA fiber production, its reliance on volatile and hazardous solvents creates scalability challenges due to high solvent waste, costly recovery, and environmental concerns. Additionally, rapid solvent evaporation prevents the necessary chain interaction for stereocomplex crystallization, leading to homo-crystallite formation instead. On the other hand, melt electrospinning offers a more industrially feasible approach, but optimizing processing conditions to ensure proper scPLA crystallization remains a key challenge. For these reasons, during this research, we address these limitations using melt-electrospinning, focusing on the spinning parameters and assessing their effect on the SC formation and the fiber diameter.