Oil recovery, retention index, and thermodynamic parameters of green coffee beans (GCB) and its press cake (PC) extraction using bio-based solvents were investigated. The extraction parameters investigated were temperature (35 to 55 °C), type of material (coffee beans and press cake), and type of solvent (ethanol, acetone, and ethyl acetate), at a fixed solvent to solid mass ratio (5:1) (w/w). The fatty acid profile of the ethanolic extract was assessed for both GCB and PC, and compared to the oil obtained from the mechanical pressing. It was observed that higher temperatures affected positively the extraction yields, especially when acetone and ethanol were employed, allowing a recovery up to 90% and 56.7% for GCB and PC, respectively. The solution retained in the raffinate phase from the GCB extraction was greater than that for the PC. For all operational levels, the ∆H and ∆S were positive. ∆G decreased with increasing temperature. Palmitic and linoleic acids were predominant in all types of oil. The oil obtained by pressing showed higher content of linoleic acid (45.32%), while the solventextracted oil from GCB had more palmitic acid (34.79%), and the PC oil presented intermediate levels of all the methyl esters.