An electrospinning method was used to spin semi-crystal line POIY(L-lactide) (PLLA) nanofibres. Processing parameter effects on the internal molecular structure of electrospun PLLA fibres were investigated by x-ray diffraction (XRD) and differential scanning, calorimetry (DSQ. Take-up velocity was found as a dominant parameter to induce a highly ordered molecular structure in the electrospun PLLA fibres compared to solution conductivity and polymer concentration, although these two parameters played an important role in controlling the fibre diameter. A collecting method of a single nanofibre by an electrospinning process was developed for the tensile tests to investigate structure-property relationships of the polymer nanofibres. The tensile test results indicated that higher take-up velocity caused higher tensile modulus and strength due to the ordered structure developed through the process.