This data set consists on the raw data corresponding to XCT tomography and WAXS 1D diffractograms for the work "Unraveling the Print-Structure-Property Relationships in FFF of PEEK: A Critical Assessment of Print Parameters". They correspond to the following Design of Experiments: PrintExperiment Nozzle T (ºC) Bed T (ºC) Chamber T (ºC) Printing Speed (mm/s) Annealing T (ºC) 1 420 100 80 15 390 2 455 100 80 15 off 3 420 150 80 15 off 4 455 150 80 15 390 5 420 100 100 15 off 6 455 100 100 15 390 7 420 150 100 15 390 8 455 150 100 15 off 9 420 100 80 60 off 10 455 100 80 60 390 11 420 150 80 60 390 12 455 150 80 60 off 13 420 100 100 60 390 14 455 100 100 60 off 15 420 150 100 60 off 16 455 150 100 60 390 Each data file is labled with the experiment number. XCT and WAXS were conducted on the same specimen. For details on the materials and methods, please relate to the associated publication. This project has received funding from the European Union’s Horizon 2020 research and 497innovation programme under the Marie Skłodowska Curie grant agreement No [101106955].