Lipase-immobilized poly(vinyl alcohol) (PVA) nanofiber was formed by electrospinning. The specific surface area of the nanofiber (3.75m2/g) was about 240 times larger than that of lipase-immobilized PVA film 0.0157m2/g). The nanofiber was used as the catalyst for the esterification of citronellol with acetic acid. The ester conversion of the nanofiber exceeded 80% after 72h at 30. The lipase-immobilized nanofiber showed higher activity for the esterification than the lipase-immobilized film and lipase powder, and more stable activity for reuse than commercially available immobilized lipase (Novozym-435), probably because it has a high specific surface area and is less affected by product water from the esterification.