In order to determine the material composition of the 3D printed shoe upper structure and to ensure the best results of 3D printed shoe uppers, the 3D printed shoe upper structure with thermoplastic polyurethane (TPU), flexible polylactic acid (PLA), and polyvinyl alcohol (PVA) as the main 3D printing materials are discussed, and the 3D printed thermoplastic polyurethane (TPU) and flexible polylactic acid (PLA) consumables are analyzed by scanning electron microscopy, infrared spectroscopy, IR, X-ray diffraction, differential thermal analysis, tensile properties and elastic recovery rate test analysis on 3D printed thermoplastic polyurethane (TPU) and flexible poly (lactic acid)(PLA) consumables, and scanning electron microscope (SEM), differential thermal analysis and solvency properties analysis on 3D printed support material poly (vinyl alcohol)(PVA), to explore the mechanical properties of these three materials. The results show that thermoplastic polyurethane (TPU) and flexible polylactic acid (PLA) materials are suitable for 3D printed shoe upper fabrics, and polyvinyl alcohol (PVA) can be used as a 3D printing support material in physical form.