Supercritical carbon dioxide (scCO2) is a non-toxic, inert, and widely used solvent in green chemistry, offering tunable properties such as density, diffusivity, viscosity, and polarity, adjustable through temperature, pressure, or co-solvent addition. This study employs the Design of Experiment (DoE) methodology to optimize scCO2-assisted synthesis of Li-S battery cathodes, presenting the first systematic investigation of how scCO2 conditions affect the structural and surface properties of reduced graphene oxide (rGO) during sulfur decoration. Results show that temperature and pressure significantly influence sulfur integration and cathode performance. By combining DoE with detailed electrochemical impedance analysis using complex nonlinear least squares fitting, the study provides deeper insight into composite electrochemical behavior under varying conditions. An optimal rGO structure with low charge transfer resistance, enabling efficient ion and electron transport, was obtained at 150 bar and 60 °C, balancing sulfur loading and pore accessibility. Conversely, harsher conditions (180 bar, 80 °C) caused sulfur agglomeration and higher resistance, reducing performance. These findings highlight the necessity of precisely controlling scCO2 synthesis parameters to enhance cathode structure and improve electrochemical performance and long-term stability of Li-S batteries.