Nanowebs consisting of interwoven ZnFe2O4 nanofibers are synthesized by a simple electrospinning technique, to be employed as an environmentally friendly anode in lithium ion batteries. Effect of precursor viscosity on the growth mechanism of electrospun ZnFe2O4 nanofibers (ZFO-NF) and ZnFe2O4 nanorods (ZFO-NR) is studied by microscopy and diffraction techniques. Structural characterization by powder X-ray diffraction, FESEM and HRTEM studies evaluates the single phase nature of ZnFe2O4, which consists of 11(3) nm nanocrystals that self-agglomerate to form nanofibers after thermal treatment. FESEM micrographs depict the self-assembly of electrospun ZnFe2O4 nanofibers into intertwined porous nanowebs with a continuous framework. Benefitting from the one-dimensional functional nanostructured architecture, the application of electrospun nanowebs with ZnFe2O4 nanofiber (ZFO-NF) anodes in lithium ion batteries exhibits excellent cyclability and retains a reversible capacity of 733(10) mAh g(-1) up to 30 cycles at 60 mA g(-1) as compared to ZnFe2O4 nanorods (ZFO-NR) with a capacity of similar to 200 mAh g(-1). In addition, the importance of providing electronic wiring during lithiation/delithiation, especially in prolonged cycling, is emphasized.