Summary: Construction of a high‐sulphur‐loading electrode is an effective approach for achieving a high‐specific energy density in lithium‐sulphur batteries. The polymer binder has an important influence on the microstructural and electrochemical behaviours of high‐sulphur‐loading electrodes. In the study, three commonly used binders, namely polyvinylidene fluoride (PVDF), polyacrylonitrile (LA133), and polyacrylic acid (PAA), were used with high‐sulphur‐loading electrodes, and their electrochemical performance characteristics were investigated. The water‐soluble binders LA133 and PAA showed significantly better performance than PVDF. The PAA binder effectively decreased the overpotential polarisation and resistance, increasing the lithium‐ion diffusion coefficient and accelerating the redox reaction of polysulphides. The CNTs@S electrode with PAA as the binder showed the first discharge specific capacity of 703 mAh g−1 at a sulphur loading of 5.1 mg cm−2 at 0.3 C, with a decay rate of 0.1% over 150 cycles. Even with a higher sulphur loading of 7.1 mg cm−2, the electrode exhibited an initial capacity of 6.3 mAh cm−2 at a current density of 1.19 mA cm−2 and capacity retention of 98.4% over 50 cycles. In addition, the electrode with the PAA binder showed significantly increased volume energy density. The aqueous PAA binder is more suitable for the fabrication of high‐sulphur‐loading electrodes for lithium‐sulphur batteries. [ABSTRACT FROM AUTHOR]