Poly(L-lactide) (PLLA) possesses one of the highest piezoelectric coefficient and electroactive response in the class of biodegradable, bio-based, and biocompatible polymers. Being a widespread and Food and Drug Administration (FDA)-approved polymer, piezoelectric PLLA is an upcoming game-changer in a wide range of biomedical applications, such as energy harvesting, monitoring, and control, and includes the development of biodegradable sensors and actuators, drug delivery and the fabrication of smart scaffolds for tissue regeneration. For many of these applications, the piezoelectric chain morphology, in the form of high optical purity, chain orientation, and degree of crystallinity, is essential for the piezoelectric response. This work presents the progress of piezoelectric PLLA, reveals the main characteristics of the piezoelectric chain morphology of PLLA, and highlights the different processing strategies to obtain piezoelectric PLLA, as well as how the piezoelectric chain morphology is identified and quantified. This enables the research community to understand, determine and process piezoelectric PLLA for their proper research activities.