Shuttle effect of the dissolved polysulfide is a main disadvantage for Li-S batteries, which has been explored by several polar materials to absorb lithium polysulfide with physical and chemical effect. Herein, for the first time, a composite of carbon nanofibers decorated with MnO nanoparticles (CNF-MnO) has been prepared by the facile electrospinning method followed by thermal treatment. SEM and TEM characterization delivered that the MnO NPs on CNF did not change the morphology but decrease the electronic conductivity of CNF-MnO composite. The CNF-MnO composite exhibited excellent electrochemical cyclic stability because of its strong chemical absorption for polysulfide. Interestingly, CNF-MnO composite served as both cathode as well interlayer for Li-S batteries. The CNF-MnO-S as cathode material showed an initial discharge capacity of 683.2 mAh g(-1) at 1.0 C and remained 592.0 mAh g(-1) even after 250 cycles with the capacity decay of 0.053% per cycle. As well, CNF-MnO as interlayer delivered superior cycling stability even at high current density of 3.0 C, where the capacity still maintained 542.2 mAh g(-1) over 200 cycles.