A cost effective, low temperature, scalable route is presented for the synthesis of Selenium nanoparticles-cetyltrimethylammonium bromide-decorated multiwalled carbon nanotubes (Se NPs@CTAB-MWCNTs) composite. The Se content in the carbon black (CB) free Li-Se NPs@CTAB-MWCNTs cell is ∼72 wt%, which is much higher than that reported in previous studies on Li-Se composite cells, where the Se loadings typically vary between 40 and 50 wt% in full cells. The high loading of Se imparts a high capacity to the composite cell due to a high electrical conductivity of Se NPs (∼0.1 S cm−1). The initial Li-ion storage capacity delivered by the same CB free cell is ∼709 mAh gSe −1 (at 0.5 current (C)-rate), and a reversible capacity of 157 mAh gSe −1 is retained after 500 cycles. In comparison, the reversible capacities offered by the Li-Se NPs-CB cell (at 80 wt% Se loading), and the Li-Se NPs@CTAB-MWCNTs-CB cell (at 64 wt% Se loading) are 13.8 and 172.5 mAh gSe −1 at the same C-rate, after 500 cycles. For the CB free cell, the capacity decay is 0.14% per cycle from 8th to 500th cycle. Though present in small quantities of 18 and 16 wt% in the two composite based cells without and with CB, CTAB-MWCNTs confer the following functional attributes to the cells. They (a) restrict polyselenide shuttle, (b) buffer the volume expansion during discharge and (c) allow Li-ion storage, without the use of any conducting CB additive (due to the composite's high inherent electrical conductivity). The electrochemical performance of the CB free Li-Se composite cell opens up opportunities to develop eco-friendly and robust Li-Se batteries.