Chia seeds have a high oil content that consists primarily of omega-3 and omega-6 fatty acids, which are essential for humans. The technique used for chia oil extraction can be influences the final quality of the oil; thus, it is highly important to study the different extraction techniques. This study aimed to determine the extraction yield from different techniques and to evaluate the oils obtained. Chia oils were extracted by pressing, cold solvent and by supercritical CO2 with/without ultrasound and co-solvent (ethanol) and the oils were evaluated for their chemical and physicochemical characteristics. In addition, the extracted oils were compared with a commercial sample. By the use of previous ultrasonic steps and the addition of a cosolvent, it was possible to increase the yield using supercritical extraction. Among all of the studied techniques, pressing, although it resulted in the highest peroxide value, was the technique that produced the best chemical quality. In addition, a simple methodology for determination of the fatty acid composition of chia oil through H-1 NMR spectroscopy was successfully applied, without need sample pre-treatment steps such as derivatization. Therefore, by evaluating the characteristics of the extracted chia oils, we determined that they can be an excellent source of omega-3 fatty acids for foods, medicines, and cosmetics.