Sb2S3/CNT composite has been synthesized through ethylene glycol-mediated solvothermal process, and binderless, free-standing, flexible anode is prepared from the composite through vacuum filtration technique. The 1-D rod-like structure of Sb2S3 prevents self-agglomeration and exhibits well-guided charge-discharge kinetics and high surface area enhancing their electrochemical performance in Li-ion batteries. The introduction of CNTs to the Sb2S3 facilitates the preparation of free-standing flexible anodes as well as buffers the volume changes that occur during repeated cycling, thereby improving the cycling stability. The Sb2S3/CNT free-standing anode exhibits a high initial discharge capacity of 930 mAhg(-1) at a current rate of 200 mAg(-1). The anode also exhibits excellent lifetime stability and rate capability by cycling at different current rates up to 1200 mAg(-1). Sb2S3/CNT anode gives a stable capacity of 443 mAhg(-1) after 100 cycles at a current density of 200 mAg(-1), while Sb2S3 rods deliver only 293 mAhg(-1) after 100 cycles at the same current rate. This free-standing flexible Sb2S3/CNT anode is highly promising in comparison with conventional graphite powder anode.