The enantioseparation of valsartan enantiomers using chiral eutectic solvents (ESs) as extractants was initially studied. The hydrophobic ESs (LM-DTTA) formed by L-menthol and (+)-Di-p-toluoyl-D-tartaric acid is a suitable chiral medium for the enantioselective extraction of R- and S-valsartan. Four principal parameters affecting chiral extraction, such as phase volume ratio, initial rac-valsartan concentration, extraction temperature, and system pH, were evaluated. The results showed that LM-DTTA has better and higher enantioselectivity levels, and one-step chiral extraction achieved an ee value of S-valsartan up to 91% under the optimized conditions. In addition, this chiral medium can be recycled through simple back-extraction with sodium bicarbonate solution and reused at least five times, giving similar results. This work provides a clear example of enantioseparation of the rac-valsartan via liquid–liquid enantioselective extraction using the LM-DTTA as a novel chiral recognition and separation medium. As a result, the established enantioselective extraction method can efficiently separate the R- and S-enantiomer and promote sustainable development for the production of S-valsartan.