We report on a novel, simple, and environmentally benign synthesis route for a free-standing reduced graphene oxide (r-GO) aerogel and its application as supporting electrode for the electrochemical redox reaction of sulphur in a catholyte-based lithium-sulphur battery. A mesoporous matrix is formed by a layers of r-GO, providing sites for electrochemical reactions and a highly conducting pathway for electrons. The highly porous structure is easily infiltrated by a catholyte solution providing a homogeneous distribution of the sulphur active material in the conductive graphene matrix and ensuring efficient electrochemical reactions. This is demonstrated by a high capacity, 3.4 mAh cm−2, at high mass loading, 3.2 mg cm−2 of sulphur in the cathode and in total the sulphur loading in the Li-S cell is even double (6.4 mg cm−2). Additionally, the presence of oxygen groups in the r-GO aerogel structure stabilizes the cycling performance and the Li-S cell with the fluorine free catholyte shows a capacity retention of 85% after 350 cycles.