The structural properties of poly(lactic-acid) PLA nanofiber scaffolds prepared by electrospinning have been correlated with their process condition. The influence of the electrospinning processing parameters on structure including fiber orientation, take-up velocity and post-thermal treatment was analyzed. The structure and the properties of the scaffolds were studied by x-ray diffraction (XRD), atomic force microscope (AFM), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), and differential scanning calorimetry (DSC). The existence of crystallinity into the nanofibres of PLA was found. The careful observation by HRTEM shows an amorphous core and a semicrystalline shell structure (supramolecular), and the surface of nanofiber observed by AFM shows a laminate periodic along the main axis of the fiber. These observations will be useful in understanding the structure-property relationships of oriented nanofibre scaffolds for medical or biological applications.