Flexible and freestanding sulfur electrode is of great importance for the fabrication of high-performance flexible lithium-sulfur batteries. However, electrodes with high sulfur loading usually exhibit unsatisfactory mechanical flexibility and inferior electrochemical stability. Herein, we report a high sulfur loading multilayer electrode with good flexibility, which is constructed using reduced graphene oxide and conductive polymer film by a simple multilayer coating method. The prepared electrode possesses high flexibility and electrochemical performance under sulfur loading of 6.1 mg cm−2 and sulfur content of 60% in the entire electrode. The electrode can even release a reversible capacity of 559 mAh g−1 after 500 cycles at a rate current density of 2 C, corresponding to a capacity decay rate of 0.057% per cycle. The stable electrochemical properties are due to the fact that conductive polymer films and reduced graphene oxide sheets could effectively inhibit the dissolution and diffusion of the polysulfide compounds.