The electrical properties of polymer materials, such as electrical conductivity and piezoelectricity, are significantly influenced by the ratio of amorphous to crystalline regions. Additionally, the alignment of added particles and formed crystallites is another factor that affects these properties. Conversely, a well-designed thermomechanical process can significantly impact the rate of change. This study investigates nanocomposite production with an optimal percentage of modified nanoparticles using a revamped electrospinning process and fully effective post-processing. Piezoelectric constant d33 of PLLA-2.5%CNT discussion was pioneered in this article. It was proved that the crystallinity percentage of nanocomposites can be improved by up to 70% by applying a suitable thermomechanical process and adding a suitable percentage of particles. The formation of the ordered phase, the creation of a special pattern for the movement of electrons, and the change in the conformation of the carbonyl group are the reasons for increasing the piezoelectric constant from 0.2 to 3 and increasing the electrical conductivity by 1000 orders of magnitude. Among other reasons, we can mention the alignment increment of polymer particles and crystallites and their way of texturizing in order to apply thermomechanical processing.