Designing and constructing an effective and efficient oxygen electrode plays a pivotal role in the successful development of lithium-oxygen (Li−O2) batteries. Herein, NiCo2S4 nanorod arrays directly grown on carbon textile (R-NCS/CT) is successfully prepared by a simple hydrothermal route and systematically studied for the first time as a free-standing electrode in Li−O2 electrochemical systems. The R-NCS/CT based Li−O2 battery achieves a low charge overpotential (1.17 V), a high discharge capacity (4506 mA h g−1), and improved cycle life (500 cycles). These improvements can be attributed to both, the unique architecture design of the electrodes for facilitating the rapid oxygen diffusion and electrolyte penetration and superior activity of oxygen electrode kinetics of NiCo2S4 nanorods. To some extent, the optimization of the catalyst composition and design of the electrode structures provide a guidance for further development of more stable and efficient cathodes for Li−O2 batteries.