Although Li-ion batteries have revitalized the energy storage platform, higher energy density for long-range applications is still a challenge. Beyond Li-ion, Li-S battery could be one of the most promising technologies, but challenges such as lithium polysulfide shuttling, sluggish reaction kinetics and low areal sulfur loading (<2.0 mg cm−2) remain. Herein, we report a multifunctional electrode composite consists of conducting polymer-carbon complex where the sulfur loading can reach as high as ∼75 wt %. Owing to high electrical conductivity and inherent heteroatom compositions of conductive polymers, composite electrodes are capable of suppressing polysulfide shuttling and enhance reaction kinetics via catalysis. As a result, these composite electrodes deliver outstanding electrochemical performance with the specific capacity of ∼1100 mAhg−1 for more than 100 cycles. A one-pot and straightforward procedure at ambient conditions to prepare these composite electrodes are demonstrated.