The development of safe and high-performance lithium (Li) metal anodes has been a challenging issue that has not been addressed for decades. In this study, we have developed a thermally stable polydopamine-treated three-dimensional (3D) carbon fiber-coated separator (P3D-CFS) using an economical and environment-friendly process. P3D-CFS has a conductive coating layer that is used as a 3D hosting structure, which does not cause morphological changes in the Li metal anode. As a result, the unit cells (LiMn2O4/Li metal) employing P3D-CFS improve the cycle performance and rate capability compared to commercial polyethylene (PE) separators. P3D-CFS maintained 83.1% of the initial discharge capacity at the 400th cycle, whereas bare PE maintains only 74.3% of the initial discharge capacity after the 250th cycle (C/2 = 0.5 mA cm−2). P3D-CFS maintains 42.8% of the initial discharge capacity at a 7C rate (7 mA cm−2), whereas only 0.19% is maintained by bare PE under the same condition. Owing to the thermally stable properties of P3D-CFS, the open-circuit voltage of the unit cells (LiMn2O4/graphite) that employed P3D-CFS is maintained for over 60 min at 140 °C, whereas the unit cells that employed bare PE show a sudden voltage drop after only 3 min.