Abstract. Fused Deposition Modeling is increasingly used for producing high-performing, creep-resistant, biocompatible, fireproof, highly-stable parts from polyether ether ketone. However, the knowledge on this process is still poor and fragmented, and the lack of relevant data inhibits many applications. In this paper, the effects of the nozzle temperature, nozzle speed and layer thickness on the properties of PEEK processed by Fused Deposition Modeling were investigated by performing indentation, tensile, Scanning Electron Microscope, Computer Tomography and Energy Dispersive X-ray Spectroscopy tests on as-built samples. The outgassing behavior was also analyzed, while the synchrotron radiation was used to characterize the structure of selected samples on a hitherto unexplored scale. The samples morphology was finally used to identify the optimal process window. The results provided new insights on the process and novel data enabling new applications.