Sterols are a group of molecules found in plants and animals, which have a number of valuable applications. The deodorization residue, referred to as “deodistillate”, was previously considered as a waste but its economical value nowadays increased due to the presence of high concentrations of sterols, tocopherols and other secondary metabolites attractive for the cosmetic, pharmaceutical or food industry. Sterols can be extracted from vegetable oil deodistillate through a variety of physical and chemical separation processes or their combination. Recently, the use of lipase enzymes has been demonstrated to separate sterols more selectively in higher yields and in milder conditions. This article reviews these lipase-assisted sterol extractions and their main advantages and drawbacks in economic and environmental terms.