Piezoelectric polymers currently attract lot of attention due to their electroactive properties combined to flexibility, rapid processing and low cost. These smart polymers convert mechanical stresses/strains (cyclic or sporadic) into electrical power and this property can be exploited to develop miniature sensors and power generation devices such as piezoelectric nano/microgenerators (PENG or piezoelectric energy harvesters). Actually, these autonomous devices could found many high-value emerging applications, in particular in the wireless communication industry with the growth of the IoT market for large-scale monitoring in various sectors. Piezoelectric materials play a crucial role in the PENG efficiency and piezoelectric biobased polymers such as poly(L-Lactide) (PLLA) could represent an interesting alternative to fluorinated polymers. Here, the use of PLLA as a smart electroactive polymer is under investigation using classical processing tools of the plastic industry. Actual results obtained in the framework of an INTERREG European project clearly display that thin PLLA films obtained by cast film extrusion followed by uniaxial stretching could develop a significant piezoelectric activity. The most important feature lies in a specific auto-polarization phenomenon that give rise a natural shear piezoelectricity avoiding the complex high-voltage poling step. Shear piezoelectricity coefficients d14 were approached and values close to 5 pC/N are observed at a particular 45°-angle from the drawing direction with significative electric powers harvested under cyclic deformations. Several prototype designs are discussed as well as structure/process/properties relationships to optimize energy harvesting performances. PLLA clearly provides an interesting alternative to fluorinated polymers with an excellent optimization potential regarding its process-induced electroactivity.