An efficient catalytic asymmetric hetero-ene reaction of 5-methyleneoxazolines with 1,2-dicarbonyl compounds (including α-ketoesters and glyoxal derivatives) was realized using Ni(II)–N,N′-dioxide complexes as the catalysts. It provides a rapid, high yielding (up to 99%) route for the preparation of 2,5-disubstituted oxazole derivatives in a highly enantioenriched form (up to >99% ee) under mild conditions.