Poly(L-lactic acid) (PLLA) fibers were fabricated by electrospinning. The effects of various electrospinning process parameters on the thermal properties, especially the crystallinity of the electrospun fibers were investigated. Thermal analysis of the fibers revealed that they exhibited degree of crystallinity ranging from 23% to 46% while that for the as-received granules was approximately 37%, suggesting that the crystallinity of electrospun PLLA fibres can be controlled by optimizing the electrospinning process. This finding is very important because crystallinity affects polymer properties such as degradation, stiffness, yield stress, modulus and tensile strength, solubility, optical and electrical properties which will in turn affect the behavior of these materials when they are utilized in energy, environment, defense and security applications. The results presented in this paper show that the degree of crystallinity of the electrospun fibers decreased with increasing the polymer solution concentration. Furthermore, an optimum electrospinning voltage at which maximum degree of crystallinity can be obtained was observed. At voltages higher or lower than the optimum electrospinning voltage, the degree of crystallinity will decrease or increase, respectively. The effect of the needle tip to collector distance (NTCD) on the degree of crystallinity follows no predictable and consistent pattern.