Abstract: Conductive polymer composites (CPC) has significant application value in flexible electronics, smart wearables and sensor devices, due to excellent electrical conductivity and mechanical flexibility. In this study, an innovative synergistic preparation strategy featuring a multi-level structure, namely “meltblown spinning- functional modification-hot-press forming”, is proposed and realized, which provides a novel design concept for high-performance flexible conductive materials. Firstly, thermoplastic polyurethane (TPU) non-woven fabric was prepared by melt-blown spinning technology as the skeleton of the conductive network. The TPU non-woven fabric was modified by carbon nanotubes (CNTs) to obtain TPU-CNTs conductive non-woven fabric. Then, it was compounded with TPU film by hot-pressing technology to prepare TPU/CNTs conductive composite film, achieving structural composite and interface fusion. The morphological structure and comprehensive performance of TPU/CNTs composite films were systematically studied by means of SEM, TG, electrical conductivity, tensile properties and organic gas response tests. CNTs are not only uniformly dispersed on the surface of TPU non-woven fabric fibers, but also penetrate into the interior and between the fibers, forming a continuous three-dimensional conductive network across scales. This special structure endows the TPU/CNTs composite film with a low percolation value and excellent electrical conductivity. When the CNTs content is only 2.4 wt%, the electrical conductivity of the TPU/CNTs composite film can reach 9.8 S/m, significantly reducing the production cost. A complete conductive network is induced in the hot-pressing process, which effectively improves the thermal stability and mechanical properties of the TPU/CNTs composite film. Compared with the pure TPU film, the tensile strength, Young's modulus and fracture toughness of the 2-TPU/CNTs composite film are increased by 151%, 164% and 119%, respectively. A synergic enhancement of electrical conductivity and mechanical properties is realized. TPU/CNTs composite membrane exhibits a high response signal in saturated vapor, with a significantly higher response to dichloromethane vapor than to acetone. It can be used to develop industrial sensors for detecting dichloromethane leakage, showing bright application prospects in the fields of chemical safety production and environmental monitoring. This research provides an effective multi-level structure design concept for the preparation of high-performance flexible conductive materials.