High theoretical capacity (1675 mA h g−1) and energy density (2600 Wh kg−1) in addition to low cost, non-toxicity and natural abundance stimulates the exploration of sulfur as a potential cathode material. However, serious capacity fade and poor reaction kinetics leads to untimely failure which prevents the practical commodification of these batteries. Here, a simple and versatile electrospinning technique has been employed to prepare a polymeric template to fabricate hollow metal oxide@metal oxide nanofibers. The hollow fibrous shell with large specific surface area is incorporated as an anchoring material comprising of distinct crystalline phases separated by amorphous domains. Meanwhile, the encapsulated metal oxide nanoparticles ensure efficient conversion of soluble polysulfides thereby, promoting the reaction kinetics and avoiding any surface passivation of anchoring material. The LSB cell with 5 % TiO2@Fe2O3 nanofiber additives delivers impressively in the rate capability test with stable capacities of 620 and 480 mA h g−1 at 1C and 2C rate, respectively. Moreover, an excellent cycling performance is attained with a fade rate of 0.092 % per cycle over 500 cycles at 0.5C-rate. The findings of this work shall provide a pathway for facile preparation of functional metal oxide composites for simultaneous trapping and conversion of polysulfide species in sulfur batteries.