<p>Environmentally-friendly thermoplastic biodegradable polyesters such as polydioxanone (PDO) are becoming increasingly available and are attracting considerable interest in the medical field due to their favourable mechanical properties and degradation to low-toxicity monomers in vivo. These properties are of particular interest in terms of their use in the field of tailored medical implants produced by means of additive manufacturing via 3D printing applying the fused deposition modelling (FDM) technique, also known as fused filament fabrication (FFF). The increasing popularity of this technology in the biomedical community is due mainly to its versatility in terms of the processing approach, structural features and final design. Practically no comprehensive studies have been conducted to date on the 3D printing of polydioxanone. Given the very limited availability of this polymer at a level of quality that allows for its medical application in humans, the aim of this study was to test the use of a commonly available polydioxanone surgical monofilament for the study of its 3D printing potential. PDO comprises a highly crystalline polymer that is susceptible to shrinkage, warpage and adhesion problems. These issues were addressed in the study together with the determination of a range of other printing parameters related to the processing of PDO for FFF 3D printing purposes. The additively produced PDO models evinced similar mechanical properties to PDO samples produced via the classical injection molding technique. Moreover, no negative impact was detected of the printing conditions on the potential degradation of the biodegradable polymer. Thus, the aim to produce PDO models with a high level of printing quality at the microscopic and macroscopic levels with real potential for use in medical applications was achieved.</p>