The continuous extraction of the rhodium inventory in supported liquid-phase (SLP) catalytic materials utilized in the hydroformylation (HyFo) of 1-butene was investigated by supercritical carbon dioxide (scCO2). Optimization of extraction efficiency involved varying parameters such as temperature (90 and 120 °C), pressure (10, 20 and 30 MPa), and the addition of methanol as a polar co-feed to the extraction medium (0–20 vol%). The results underscored the critical role of methanol in facilitating extraction, as experiments employing pure scCO2 yielded no rhodium recovery. Furthermore, extraction performance demonstrated sensitivity to temperature and pressure adjustments during the process. Notably, the use of 10 vol% methanol at 120 °C and 30 MPa achieved complete rhodium extraction from the grained SLP materials, which was identified as the optimum extraction condition. This study highlights the potential for scaling up in-situ rhodium extraction processes within HyFo production plants based on SLP catalysts, emphasizing significant implications for industrial applications.