The production of porous scaffolds has been widely investigated by the scientific community due to its suitability for tissue engineering. Among techniques that allow the fabrication of porous materials, electrospinning is appealing for being robust and versatile. This research investigated the pore formation in poly (L-co-D,L lactic acid) fibers obtained by conventional electrospinning and the influence of chloroform as a single solvent on fiber morphology. Random and highly porous fibers with a mean diameter of 2.373 ± 0.564 µm were collected. Chloroform affects the fiber morphology, mainly for its fast evaporation and low density of charges. The solvent on the surface evaporates quickly, and the low stretch of the jet does not help the polymer to reorganize over the length of the fiber, forming pores. In conclusion, the low dielectric constant and boiling point of chloroform induce pores formation along the PLDLA fibers.