Capsaicin (CC), the dominant pungent compound in hot chilies, is widely used as a flavouring agent, preservative, active compound in packaging film and functional foods. Capsicum chinense cv Bhut Jolokia is one of the richest sources of CC, yet scarcely studied. The present investigation aimed to optimize a clean and green method for extracting CC through supercritical fluid extraction (SFE) method. Low-grade, culled, and discarded fruits were used for the extraction, and process was optimized through central composite design of RSM. The optimized extraction condition, 68.31 ℃/347.98 bars/102.50 min, resulted in maximum CC content (367.14 ± 1.12 mg/g) and oleoresin yield (7.23 ± 2.15 %) in a shorter extraction time (< 2 h). Accelerated thermal stability study suggested first-order degradation kinetics of CC at temperatures from 80 to 140 ℃. The activation energy (kJ/mol) of the reaction was 71.86, while Q10 for 80 to 100 ℃, 100 to 120, and 120 to 140 were 0.0548, 0.0574, and 0.1456, respectively. Valorisation of Bhut Jolokia for targeting an oleoresin with maximum CC opens a new window for its commercial exploitation in food industry. Furthermore, the study opens avenues for exploration of SFE-based extraction as clean, and sustainable method with reduced carbon footing.