Polycaprolactone (PCL) is one of the earliest, commercially available, synthetic polymers characterized by a large set of biodegradation and mechanical properties that can be finely controlled by regulating the local environmental driving forces (ie, microorganisms, enzymes, hydrolysis). Owing to their faster resorbability and long-term degradation in the presence of water (up to 3 to 4 years), PCL has been widely investigated as a bioinspired material able to target selective cell response via controlled intracellular resorption pathways. In comparison with other aliphatic polyesters, the superior rheological and viscoelastic properties render PCL easy to manufacture and manipulate into a wide range of three-dimensional platforms (ie, porous scaffold, micro- and nanocarriers, and implantable devices). In this article, we discuss the main relationships between polymer synthesis, physical/chemical properties, and processing conditions to optimize the fabrication of biodegradable devices made of PCL, putting particular focus on drug delivery, tissue engineering. and green chemistry applications.