Defective green coffee beans are typically discarded due to their negative impacts on coffee qualities compared to normal beans. However, there are some types of defective beans that can cause volatile aroma compounds after roasting similar to those produced by normal beans. This study aimed to optimize conditions for coffee oil extraction by supercritical carbon dioxide using the response surface methodology (RSM). Furthermore, the investigation assessed the aroma-active compounds and sensory quality in extracted coffee oil. Thus, operational temperatures (33.2–66.8 °C), pressure (10–30 MPa) and ethanol (g) to roasted coffee (g) ratio (0.25:1–1.5:1) were optimized for coffee oil extraction. As a result, different oil yields with different key volatile aroma compounds concentrations were obtained and it was found that the optimum conditions for extraction were a temperature of 50 °C, pressure of 30 MPa, and ethanol (g) to roasted coffee (g) ratio of 1:1 to obtain 6.50% (w/w) coffee oil yield. Key volatile aroma compounds, including furfuryl alcohol, 5-methyl furfural, 2,5-dimethylpyrazine, 4-vinylguaiacol, furfuryl acetate, 3-ethyl-2,5-dimethylpyrazine, thiazole, 1-furfurylpyrrole, pyridine, 2,3-butanediol, and 3-methyl-1,2-cyclopentanedione which contributed to the most preferable burnt, sweet, bready, chocolate-like, and roasted flavors, were quantified. Overall, the results suggested that coffee oil extracted from defective beans could be potentially used as a flavoring agent.