Supermolecular complexation with cyclodextrins by non-covalent host-guest interaction is used for various applications. In this work, we fabricated the freestanding and flexible core-shell MnO/carbon nanofiber (CNF) composite thin films by host-guest interaction and high-voltage electrospining technique. The as-prepared composite thin film with dual carbon layer nanofibers showed smaller MnO particle size, lower electron-transfer resistance, and faster lithium ion migration, which were attributed to intermolecular non-covalent assembling behavior among polyacrylonitrile (PAN), beta-cyclodextrin (beta-CD) and Mn ion. As expected, the composite film as anode in Li-ion battery showed impressive performance: a high reversible capacity (similar to 1025 mAh g(-1) at similar to 0.1 A g(-1)), excellent rate capability (similar to 376 mAh g(-1) at similar to 5 A g(-1)), and superior cyclability (similar to 844 mAh g(-1) at the current density of similar to 1 A g(-1) after 800 cycles). Such outstanding electrochemical performance endows the MCNFs composites with great potential as anode material for LIBs. (c) 2017 Elsevier Ltd. All rights reserved.