An electrospinning technique based on the use of two oppositely charged nozzles was applied to fabricate continuous twisted yarns of poly(L-lactide) (PLLA) nano/micro fibers. In this study, the effect of solvent on the electrospinning of PLLA fibrous yarns was investigated. For this purpose, yarns were electrospun using chloroform, dichloromethane or 2,2,2-trifluoroethanol as solvents at a PLLA concentration of 7 wt%. The analysis of the morphology, diameter, crystallinity and mechanical properties of electrospun yarns revealed that the vapor pressure of the solvent plays an important role. Whereas the fiber diameter decreased, the crystallinity of the fibers increased using a solvent with lower vapor pressure. In addition, mechanical properties (e.g., tensile strength and modulus) revealed that the yarns composed of fibers with smaller diameters showed higher tensile strength and modulus. In summary, fine-tuning solvent properties resulted in a modulation of fiber diameter, crystallinity, and thereby yarn mechanical properties, and are important factors to consider in the fabrication and application of electrospun yarns.