Polyunsaturated fatty acids (PUFAs) have various physiological functions. O
f these, ethyl eicosapentaenoate is industrially purified and used as a med
icine. Other PUFAs, such as docosahexaenoic acid (DHA), gamma -linolenic ac
id (GLA), and arachidonic acid (AA), are also expected to be used as pharma
ceutical agents; however, their industrial purification processes have not
been established. Because PUFAs are highly unstable against heat and oxidat
ion, we attempted to purify them by taking advantage of their enzymatic rea
ctions. When free fatty acids (FFAs) originating from PUFA-containing oil w
ere selectively esterified with lauryl alcohol (LauOH) using a lipase actin
g on a desired PUFA very weakly, the PUFA was efficiently enriched in the F
FA fraction. In addition, when selective alcoholysis of ethyl esters origin
ating from PUFA-containing oil with LauOH was carried out, the PUFA ethyl e
ster (EtPUFA) was enriched to a desired purity in the unreacted ethyl ester
fraction. These reaction mixtures contain LauOH, PUFA (EtPUFA), and lauryl
esters, and their molecular weights are different from one another. Hence,
PUFA or EtPUFA can be easily separated by conventional distillation. Selec
tive esterification increased the purity of DHA, GLA, and n-6 PUFAs rich in
AA to 91, 98, and 96 wt%, respectively. Selective alcoholysis was also eff
ective for increasing the purity of ethyl docosahexaenoate to 90 wt%.