In this study, the production of hollow Polybutylene Succinate (PBS)/Thermoplastic Polyurethane (TPU) nanofibers as biodegradable nanomaterials with improved mechanical properties were carried out by coaxial electrospinning method. The polymer solutions of pure PBS, pure TPU, and PBS/TPU blends (60/40, 40/60, 20/80 w/w) (as the shell) versus pure Polyvinylpyrrolidone (PVP) (as core) were put together for bi-component nanofibers production. The core structure of nanofibers was dissolved in distilled water. Thus, hollow nanofibers were obtained with the removal of PVP from the structure. Characterization studies (SEM, FTIR, and Tensile tests) of hollow nanofibers were performed. The morphological properties of PBS/TPU blends in ratios of 60/40 and 20/80 were observed as homogeneous and non-adhered fiber structures. It was determined that the hollow PBS/TPU (60/40) mat has the thinnest nanofibers. New bond formations within the interactions of substances as studied in the chemistry of blended electrospun webs were examined with FTIR analysis. Therewithal, this test showed the removal of PVP in the core of all nanofibers. It was observed that the adhered fibers increased the tensile stress and decreased the tensile strain at mechanical test results that were verified also by SEM views. It is suggested that the hollow nanofibers produced by this study can be used in the biomedical field as a biodegradable and breathable wound dressing.