We reported the synthesis of dendrite-like carbon nanotube-confined polymeric sulfur composite by modifying the surface of carbon nanotubes (CNTs) with trithiocyanuric acid (TTCA) and then copolymerizing with sulfur. DSC results show the successfully formation of robust chemical bonds between sulfur and TTCA modified CNTs, which effectively avoid the dissolution of polysulfide when used as cathodes for lithium–sulfur batteries. The composite with a high sulfur content of 78 wt% exhibits an initial charge capacity of 698 mAh g− 1 and the residual capacity of 553 mAh g− 1 after 1000 cycles at a rate of 1 C.