In this work, we design and fabricate a novel Ni-NiO-C@CNT composite with synergetic features combining a new metal organic framework-Ni-Benzimidazole (Ni-PhIm) derived Ni-NiO-C and high conductive carbon nanotube (CNT). The Ni-NiO-C was synthesized by carbonizing Ni-PhIm, which used benzimidazole as the organic ligand. The carbon skeleton of Ni-NiO-C provides numerous active sites for adsorbing and chemical anchoring for polysulfides. Meanwhile, the uniformly dispersed Ni and NiO in Ni-NiO-C ensure the integrity of the internal redox process. In addition, the interconnected CNT networks offer good conductivity throughout the entire structure, contributing to fast electron transfer. Hence, the Ni-NiO-C@CNT@S electrode exhibits a remarkable initial specific capacity of 1468 mAh g−1 at 0.2 C, and maintains 904.4 mAh g−1 even at a high discharge rate of 2 C. Moreover, Ni-NiO-C@CNT@S presents outstanding cycle stability with capacity retention of 76.20% and a decay rate of 0.05% per cycle after 500 cycles at 2 C. This work provides a new avenue and an excellent example to design and fabricate cathode material of LSB with outstanding ion/charge transmissive capability to enhance electrochemical performance.