Polylactic acid (PLA) is one of the known synthetic polymers with potential piezoelectric activity but this property is directly related to both the crystalline structure and crystalline degree. Depending on the process conditions, PLA can crystallize in three different forms: α-, β-, and γ- form, with β-crystalline phase being the piezoelectric one. To obtain this crystalline structure, transformation of α to β is required. To do so, the strategies followed so far consisted in annealing or/and stretching of previously obtained PLA in the form of films or fibers, that is, additional post-processing steps. In this work, we are able to obtain PLA fibers with high macromolecular alignment, as demonstrated by SEM, and in the β polymorph, as detected by X-ray diffraction (XRD) without the requirement of post-processing. For that, PLA fibers were prepared by using an electrospinning coupled to a drum collector. This set up and the optimization of the parameters (voltage flow-rate, and drum collector speed) induced molecular stretching giving rise to uniaxially oriented and highly aligned fibers.