Recently, the multi-level structure materials with some superior performances has attracted broad attentions. In this study, the elastomeric tree-like thermoplastic polyurethane (TPU) nanofiber membranes with multilevel structure were prepared by introducing tetrabutylammonium chloride (TBAC) via onestep electrospinning. The coverage rate and average diameter of the TPU tree-like nanofibers could be controlled by varying the solution concentrations and electrospun parameters. The special multilevel structure with trunk fibers (diameter 300-500 nm) and branch fibers (diameter 20-80 nm) significantly improved crystallinity, hydrophilicity and flexibility performances comparing with pristine TPU nanofibers, and the novel hierarchical elastomeric tree-like nanofiber membrane had a bright future in various potential applications, such as medical, filtration and protective field, etc. (C) 2017 Elsevier B.V. All rights reserved.