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This work presents a way to use ethanol and spent coffee grounds (SCG) as feedstocks for biodiesel production to solve ethanol overproduction in Thailand and biodiesel feedstock shortage problems together. Waste coffee oil (SCGO) was ethanolic extracted from SCG; then, ethanol-SCGO mixture was transesterified in supercritical condition without ethanol removal. The ethanolic extraction curves of SCG at a temperature range of 50–70 °C were constructed. Transesterification experiments were studied in a batch reactor and a continuous reactor at various temperatures (275–350 °C) and reaction time (5–40 min) under 15.0 MPa. The molar ratio of ethanol-oil mixture was set at 30:1. The highest ester content of 88.37 ± 3.00 wt% was found in biodiesel obtained at a temperature of 275 °C and a reaction time of 40 min in a batch reactor. Furthermore, excess temperature (< 300 °C) and reaction time (< 20 min) induced thermal degradation and promoted the loss of ethyl linoleate. For continuous reactor, the maximum ester content of 83.38 ± 5.86 wt% was observed at 325 °C and 29.4 min of residence time. Unlike in batch reactors, thermal degradation of ethyl linoleate was not observed in a continuous reactor. The results showed that ethanolic extraction and supercritical transesterification are alternative ways to produce biodiesel from SCG without removing extractant and using catalyst. From a prospective point of view, techno-economic analysis (TEA) and life-cycle assessment (LCA) of invented process should be conducted to ensure profitability and environmental benefits, respectively. [ABSTRACT FROM AUTHOR]