Abstract: In order to improve the barrier and antistatic properties of thermoplastic polyurethane (TPU), original carbon nanotubes (CNTs) were added into functional modification reduced graphene oxide (FRGO), and hybrid particles FRGO-CNTs which were uniformly dispersed in N, N-dimethylformamide (DMF) were prepared by non-covalent modification firstly. Then, FRGO-CNTs/TPU composite films were fabricated by solution coating method on the coating machine. Finally, the structures and properties of FRGO-CNTs/TPU composite films were characterized by FTIR, XRD, XPS, FE-SEM, TG, oxygen transmission rate tester, high resistance meter and universal testing machine. The results demonstrate that FRGO and CNTs produce synergistic effect through π-π conjugation, and the prepared FRGO-CNTs show good compatibility with TPU matrix. When FRGO-CNTs content (using TPU as reference) is 2.0wt%, the thermal decomposition temperature of composite film increases by 49℃, and the oxygen transmission rate decreases by 53.7%. The FRGO with large specific surface area and the CNTs with high length to diameter ratio can build the conductive network in TPU matrix. When FRGO-CNTs content is only 0.8wt%, the volume resistivity of FRGO-CNTs/TPU composite film declines by as much as 7 orders of magnitude. Meanwhile, with the FRGO-CNTs content increasing, the tensile strength and elongation at break of composite films both rise at first and then go down.