Catalytic enantioselective Baeyer-Villiger (BV) oxidations of racemic and meso cyclic ketones were achieved in the presence of chiral N,N'-dioxide-Sc-III complex catalysts. The BV oxidations of prochiral cyclohexanones and cyclobutanones afforded series of optically active epsilon- and gamma-lactones, respectively, in up to 99% yield and 95% ee. Meanwhile, the kinetic resolution of racemic 2-arylcyclohexanones was also realized via an abnormal BV oxidation. Enantioenriched 3-aryloxepan-2-ones, whose formation is counter to the migratory aptitude, were obtained preferentially. Both the lactones and the unreacted ketones were obtained with high ee values.