NASICON frame work Na3V2(PO4)(3) (NVP), wrapped by nitrogen and sulfur doped bio-carbon matrix derived from human hair (HHC) has been investigated for its anode behavior in SIBs. Basically, NVP is bestowed with a crystal structure of 3D open framework and a moderate theoretical capacity of 118 mAh g(-1), which are the twin advantages and motivation behind the selection of this material. Prepared through a simple, scalable and facile method, the key problems associated with pristine NVP electrode material, such as inferior conductivity and severe volume change have been mitigated to a great extent through the formation of a composite containing HHC. Herein, HHC is a cheap and eco-friendly composite additive, obtained from a universal bio-waste, viz., human hair and hence NVP/HHC qualifies itself as a green composite. Interestingly, NVP/HHC-10 (in-situ) and NVP/HHC-20 (ex-situ) anodes show excellent electrochemical performance in terms of cycling stability up to 500 cycles and rate capability @ 2 A g(-1), which are superior than similar category NVP anodes reported in the literature. Further, post cycling structure and morphology of NVP/HHC composite anodes evidence the appreciable stability bestowed with the select composition, which is found to get maintained upon extended cycles and even after rate capability test. (C) 2016 Elsevier B.V. All rights reserved.